IE47254B1 - Phenylurea derivatives - 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 new and valuable N-phenylN'-methyl-Ν'-methoxyurea derivatives having a good herbicidal action and to herbicides containing these compounds as active ingredients.

U.S. 2,655,447, German Laid-Open Application DOS 2,107,77^ and German Laid-Open Application DOS 2,039,041 disclose that N-(4-isopropylphenyl)-N',Ν'-dimethylurea is well tolerated by winter wheat. It also removes unwanted grasses, such as Alopecurus myosuroides, and some broadleaved species. However, its action on Galium aparine and other dicotyledonous species is completely unsatisfactory.

The corresponding N-(4-isopropyIphenyl)-N*-methoxy-.”'-methylurea (disclosed in German 1,062,059) has a similar herbicidal action.

The compound N-(3-tert-butylphenyl)-N',Ν'-dimethylurea disclosed in German Laid-Open Application COS 2,436,108 has an intensive herbicidal action. However, it is tolerated to an insufficient extent by cereals. The compound M-(3-methyIphenyl)N’-methoxy-N’-methylurea disclosed in German Laid-Open Application - la47254 DOS 1,905,598 has on average a somewhat weaker herbicidal action, combined with a somewhat more favorable but very marginal selectivity in cereals.

We have now found, surprisingly, that methoxynethylurea derivatives of the formula where R denotes branched alkyl of from 3 to 5 carbcn atoms (e.g., isopropyl, isobutyl, sec-butyl, tert-butyl, 1,1-dimethylpropyl, l-ethylpropyl, 1-methylbutyl, 2,2-dimethylpropyl, 2-methylbutyl or 3-methylbutyl), have a very good herbicidal action on unwanted monocotyledonous and dicotyledonous (grassy and broadleaved) plants including Galium aparine, and are excellently tolerated by cereals, especially winter cereals (rye, wheat, barley), upon both preemergence and postemergence application.

The compounds according to the invention are novel and may be prepared by the following routes. 1) An aniline of the formula II, where R has the above meaning, is converted by conventional methods with the aid of phosgene into the corresponding aryl isocyanate of the formula III which is reacted, in the presence or absence of a solvent or diluent, with hydroxylamine or a salt thereof; if a salt of hydroxy amine is used, an organic or inorganic auxiliary base is also employed. The N-aryl-N'-hydroxyurea of the formula IV obtainable - 2 4725 4 in this manner is converted into the compound I according to the invention by a conventional method in the presence of organic or inorganic auxiliary bases in a solvent or diluent with a strong methylating agent, e.g., dimethyl sulfate.

HK R II CO Cl, -M (0)-^ , R III (CHg)2S0a ^O^-KH-C-N R . I /CE3 OCH, Instead of hydroxylamine or a salt thereof, it is also possible to use N-methylhydroxylamine or 0,iH-dimethylhydroxylamine or their salts; if dimethylhydroxylamine is used, subsequent methylation is of course not carried out. 2) An aniline of the formula II is reacted in the presence of a solvent or diluent with N-methoxy-N-methylcarbamic acid chloride of the formula V with the addition of an organic or inorganic auxiliary base: •NH, + Cl-C-M/CH3 OCH, <0>-mh-c-n r~/ o ra3 ora, R II The anilines of the formula II used for producing the ureas according to the invention may be prepared for instance by the process of H.G. Gilman et al, J. Org. Chem., 19, 1071, 1959. -347254 Route 1 is preferred.

Examples of suitable anilines are m-tert-butylaniline (b.p. (0.01 mm) = 73°C) and m-isopropylaniline (b.p.(0.01 mm) = 65°C).

EXAMPLE 1 At 20° to 40°C, 12.4 parts (by weight) of N-methoxy-N-methylcarbamic acid chloride is dripped into a solution of 14.9 parts of m-tert-butylaniline and 10.1 parts of triethylamine in 100 parts of toluene. After the reaction mixture has been stirred for 30 minutes, it is washed with water, the organic phase is separated and evaporation is effected.

After recrystallization from methylcyclohexane, there is obtained 17.2 parts of N-m-tert-butylphenyl-N'-methoxy-M'-methylurea; m.p.: 82°-83°C.

EXAMPLE 2 At 0° to 5°C, 330 parts of a 33* strength sodium hydroxide solution is dripped into a stirred mixture of 287 parts of hydroxyl amine hydrochloride, 367 parts of water and 770 parts of dichloromethane. Subsequently, a solution of 443 parts of m-isopropylphenyl isocyanate in 400 parts of dichloromethane is dripped in, and the mixture is stirred overnight at room temperature. The precipitate is removed by suction filtration, washed with water and dried. There is obtained 505 parts of N-m-isopropylphenyl-N'hydroxyurea; m.p.: 12O°-123°C. This is suspended in 1,350 parts of water, and dissolved by dripping in 1,000 parts of strength sodium hydroxide solution. While stirring, 920 parts of dimethyl sulfate is dripped in at from 20° to 40°C, the mixture is stirred - 4 47254 for 1 hour at room temperature and then cooled to 5°cj and the precipitate is suction filtered, washed with water and dried.

There is obtained 48O parts of N-m-isopropylphenyl-N'-methoxyN'-methylurea, which melts, after reerystallization from methylcyclohexane, at 78°-79cC.

Suitable application methods for the new active ingredients are incorporation into the soil, treatment of the soil surface, and treatment of emerged plants. Special applications, such as post-directed or lay-by treatment, are also possible. In this case, the spray is directed in such a manner that the leaves of the emerged, sensitive crop plants are if possible avoided, and the agents reach the soil surface or unwanted plants growing beneath the crop plants.

In view of the many application methods possible, the agents according to the invention, or mixtures containing them, may be used not only on the crop plants listed in the tables, but also in a much larger range of crops for removing unwanted plants. Depending on the object to be achieved, the application rates vary from 0.1 to 15 kg/ha.

The following examples demonstrate how grassy and broadleaved unwanted plants are controlled by the agents according to the invention in winter cereals, and how well they are tolerated by the crop plants. Experiments were carried out in the greenhouse and in the open. 1. Greenhouse experiments The vessels employed were plastic flowerpots having a volume of 300 cm·5, and which were filled with a sandy loam containing - 5 47254 about 1.5% humus. The seeds of the test plants (cf. Table l) were sown shallow, and separately, according to species. For the preemergence treatment, the active ingredients were applied to the surface of the soil immediately after the seeds had been sown.

The compounds were emulsified or suspended in water as vehicle, and sprayed through finely distributing nozzles. After the agents had been applied, the vessels were lightly sprinkler-irrigated to induce germination and growth and to activate the chemical agents. Transparent plastic covers were then placed on the vessels until the plants had taken root. The cover ensures uniform germination of the plants, insofar as this is not impaired by the chemicals, and prevents readily volatile substances from escaping.

For postemergence treatment, the plants were first grown to a height of 3 to 10 cm, depending on the growth shape, before being treated. The vessels were not covered after treatment. The pots were set up in the greenhouse. The experiments were run for from 4 to 6 weeks. During this period, the plants were tended and their reactions to the various treatments assessed. The following tables contain the compounds investigated, the application rates in kg/ha of active ingredient, and the plants used for the tests. The scale used for assessment was 0 to 100, 0 denoting no damage or normal emergence, and 100 denoting nonemergence or complete destruction of at least the visible plant parts. 2. Experiments in the open The experiments were carried out on small plots with loamy sand and loam (pH 5 to 6), the humus content being from 1 to 1.5%.

In the preemergence treatment, the compounds were applied either immediately after the crop plants had been sown or up to 3 days - 6 47254 thereafter. In the postemergence treatment, the plants had cotyledons to several true leaves. However, the cereal plants or the unwanted grasses were still in the tillering stage. The weed flora was made up of a wide variety of species, and was natural. The substances were emulsified or dispersed in water as vehicle, and applied by means of a motor-driven plot spray mounted on a tractor. Naturally occurring.precipitation was sufficient to ensure germination and growth of the crop plants and weeds. All the experiments were run for several months. During this period, assessments on the 0 to 100 scale were made at certain intervals.

Results Tables 2 to 8 contain the results. The compounds according to the invention are characterized by their good action on a wide range of unwanted plants. Tolerance of them by winter cereals is also good. Compared with the prior art compounds used, the compounds according to the invention exhibit a much better control of broadleaved plants, which are mainly species which previously had been difficult to combat with cereal-selective urea derivatives. A second advantage of the new compounds is that they are not as phytotoxic as prior art compounds. - 7 47254 W Ρ C φ Η α «Ρ Μ Φ Ρ α ο Ρ ω •rt Φ ε Φ β c ο ε ε ο ο ϊ φ β rrt (0 β P •rH w Φ n Φ ed n n •rt τ: P β β CQ XJ φ X hC Φ ed r-i P Φ o p p β o (rt fl φ C β ω to XJ P rrt Φ ed XJ Φ P fl rt P a β P Φ Φ Φ £ σ ed • fl S > fl Ό o CQ rt P Φ 1 C Φ ε cd PR i c fl rt H ϋ P (rt fl 'C cd fl fl 4- •rt rt cd cd cd ¢0 φ o n c n rt p W υ P XJ fl fl 03 o O •rl >i p CQ ε cd Φ •rt (rt > P o φ cd Φ fl P fl P 0 P fl rt <.rt < o •rt > ε fl a P ed P • rt O rrt hC £ •rt rt • V. fl o * 03 • ε fl • φ rt 0 fl P fl c •rt P Φ Φ P £ fl P o < < c K 60 fl fl (rt rt rt a fl fl. rt > • ε CQ ε a c a φ •rt •rt XJ rt «rt fl rt rt 0 ϋ O P Φ X? •H rt O •rt fl fl 3 rt CQ φ O •rt fl ε P « rt £ 1 rrt a cd a co rt Φ a •rt •rl o ε Φ c Φ φ rt rt c. P P P 0 P rt o rt fl Eh ca < < •rt frt rt rt rt fl tc 0 •rt ε frt P a 03 fl fl X) 3 •rt φ Φ (rt fl > φ fl > rt ϋ fl a rt rt •rt b3 rt ε rt fl fl rrt • fl o a 0 rt 3 fl fl •rt ‘rt rt rt fl > fl 03 fl XJ P ta rt CQ CQ 0 o 0 ε fl fl o CQ ε a ε Φ rt 0 c C a φ a > fl c •rt •rt •rt Ό •rl rt Φ Φ p rrt rt fl ε fl fl P CJ rt rt O rt rt < o e e K j Polygonum persicaria Polyg. per3. ladysthumb Stellaria media ehickweed Triticum aestivum Tritic. aest. wheat Veronica spp. speedwell.

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O CJ f-CO cc CC C* O cj t— i— m in co I cr. C—00 cc co o\ in co co o coco co o\ oo O cj Occ OCO • <3 « * v4 tM rM r-! •ri t* X o . P fl Φ P σ· X X o rA X X o o o fl o •Η P fl fl fl rt Ό Φ >5 Ο fl Ρ P M rt φ Φ Φ hOXJ P rt 5 ε w fl rtP Ό C Φ rt P OH £ £ fl H 5 il II + ΟΟ ο τΗ The new herbicidal substituted urea derivatives according to the invention may be mixed and applied together with numerous representatives of other herbicidal or growth-regulating active ingredient groups. Such combinations broaden the spectrum of action, and sometimes result in synergistic effects being achieved. Examples of active ingredients which give useful compositions when mixed with the new compounds are as follows: R H H H H H and salts Cl and-salts R and salts CH^ and salts H t H and'salts i-C^ - 16 47254 C1~O^CH2_ F ' 2 RA-C-C-O-R I II Y 0 X Cl CH, R“ CH, C2H5 ch^ ch.

Cl X N-^-N ί-<γ7C2H5 C2H5 C2H5 ~C2H5 -C(CH3)2CN -ch-ch2-och3 CH, C2H5 Cl Cl Cl Cl tert. CitHg X Br Λ1 Br R jj and salts H and salts Q^N-^~~^-ON=CH-^ OH and salts X Br X = NOg CN H\ /CH3 r—λ N-C-N H3C0^O/ ° ^CH3 Cl X ^CH3 tert. N-N=CH-CH ^CH, SCH, 1 R2 R3 C-CH, 1, * se.c.CjjHg H 0 C-CH, tt J tert.CjjHg H 0 CH 3 H salts s e c. CjjH^ H salts - 19 - Η Br CH, CH, CHj CH^ X CH3OSO3 CHjOSOj ch3oso3 CP^SOj COOH and salts, esters Cl Η Cl Cl Cl Η OCHj Cl Cl Cl Cl OCHj R2 R1-O-CH-C-O-R3 w 0 R1 R2 R3 Cl-Q- XC1 H H salts, esters,amides Cl-Q- 'Cl ch3 H salts, esters, amides d-Q- ^CH3 H H salts, esters, amides CH Η salts, esters, amides Cl CH H salts, esters, H salts, esters, and salts, esters and salts, esters ci-O-o-ch^ch^-cooh ^ci and salts, esters amides amides C1-Z3“0-CH2-CH2~CH2COOH ^•ch3 and salts, esters NO * / 2 c-3 M HgC M02 CH ,C2rig K It is also useful to apply the compounds according to the invention, either alone or in combination with other herbicides, together with other crop protection agents, e.g., agents for combatting pests and phytopathogenic fungi, and plant growth regulators. The new compounds may also be mixed with mineral fertilizer solutions used to eliminate nutritional or trace element deficiencies.

Application may be effected for instance in the form of directly sprayable solutions, powders, suspensions (including high-percentage aqueous, oily or other suspensions), dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forrrs of application depend entirely on the purpose for which the agents are being used; in any case they should ensure a fine distribution of the active ingredient. 47354 For the preparation of emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, etc. and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., and strongly polar solvents such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. are suitable.

Aqueous'formulations may be prepared from emulsion concentrates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil dispersions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possible solvent or oil.

Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalenesulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of sulfated fatty alcohol - 23 47254 glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenol polyglycol ethers, alkylaryl polyester alcohols, isotridecyl alcohols, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxy10 propylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methyl cellulose.

Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.

Granules, e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicic acid, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.

The formulation contain from 0.1 to 95, and preferably 0.5 to 90, * by weight of active ingredient. - 24 There may he added to the compositions or individual active ingredients oils of various types, wetting agents or adherents, nematocides, bactericides, and antifoams (e.g., silicones). These agents may be admixed with the herbicides according to the invention in a weight ratio of from 1:10 to 10:1. The same applies to oils, wetting agents or adherents, fungicides, nematocides, insecticides, bactericides and growth regulators.

EXAMPLE 3 parts by weight of the compound from Example 1 is mixed with 10 parts by weight of N-raethyl-ti-Ryrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.

EXAMPLE 9 parts by weight of the compound from Example 2 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide to 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 90 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.022 by weight of the active ingredient.

EXAMPLE 5 parts by weight of the compound from Example 2 is dis-solved in a mixture consisting of 90 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight - 25 47254 of the adduct of 7 moles of ethylene oxide to 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained containing 0.02? by weight of the active ingredient.

EXAMPLE 6 parts by weight of the conpound from Example 2 is 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 between 210° and 280°C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02? by weight of the active ingredient.

EXAMPLE 7 parts by weight of the compound from Example 2 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-A-sulfonie acid, 17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquid is obtained containing 0.1? by weight of the active ingredient. - 26 47254 EXAMPLE 8 parts by weight of the compound from Example 1 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3? by weight of the active ingredient .

EXAMPLE 9 parts by weight of the compound from Example 2 is intimately mixed with a mixture consisting 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. A formulation of the active ingredient is obtained having good adherence.

EXAMPLE 10 parts by weight of the compound from Example 1 is intimately mixed with 10 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water to give a stable aqueous dispersion. Dilution in 100,000 parts by weight of water gives an aqueous dispersion containing 0.04wt of active ingredient.

. EXAMPLE 11 parts of the compound from Example 2 is intimately mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polygiycoi ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.

Claims (9)

1. N-Phenyl-N'-methyl-N'-methoxyurea derivatives of the formula where R denotes branched alkyl of from 3 to 5 carbon atoms.

2. N-(3-tert-Buty1 phenyl )-Ν'-methoxy-Ν'-methy lurea.

3. N-(3-Isopropylphenyl)-N'-methoxy-N'-methylurea.

4. N-(3-sec-Butylpheny1)-N'-methoxy-N'-methylurea.

5. N-(3-Isobutylpheny1)-N'-methoxy-N'-methylurea.

6. A herbicidal composition comprising a solid or liquid carrier and an N-phenyl-N'-methyl-N'-methoxyurea derivative as claimed in any of claims 1 to 5.

7. A process for controlling the growth of unwanted plants, wherein the plants or the soil are treated with an N-phenyl-N'-methyl-N'-methoxyurea derivative as claimed in any of claims 1 to 5.

8. A process for combating monocotyledonous and dicotyledonous weeds in cereal crops wherein the crop area is treated preemergence or postemergence with an N-phenyl-N'methyl-N'-methoxyurea derivative as claimed in any of claims 1 to 5.

9. A process as claimed in claim 8, wherein the cereal is wheat or barley.