CA1100530A

CA1100530A - Phenylurea derivatives

Info

Publication number: CA1100530A
Application number: CA310,387A
Authority: CA
Inventors: Friedrich Linhart; Bernd Zeeh; Peter Jacobs; Bruno Wuerzer
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1977-09-01
Filing date: 1978-08-31
Publication date: 1981-05-05
Also published as: PL107711B1; CS197329B2; ZA784967B; PT68475A; EP0001225A1; DK145171C; IL55440A; IT1106117B; AU518310B2; AU3926778A; DE2739349B2; DE2739349C3; BR7805661A; DK145171B; DE2739349A1; HU175570B; NO782922L; JPS5446745A; DD138499A5; ES472997A1

Abstract

ABSTRACT OF THE DISCLOSURE:

N-Phenyl-N'-methyl-N'-methoxyurea derivatives of the formula:

Description

O Z. 32,768 ~ENYLU~E~ DERIV~TI~v~S
The present invention relates to new and valuable N-phenyl-N'-methyl-N'-methoxyurea derivatives having a ~ood herbicidal action and to herbicides containing these compounds as active ingredients.
U.S. 2,655,447, German Laid-Open Application DOS 2,107,774 and German Laid-Open Application DOS 2,039,041 disclose that N-(4-isopropylphenyl~-N',N'-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 ccmpletely unsatisfactory.
The corresponding N-(4-isopropylphenyl)-N'-methoxy-N'-meth~l-urea (disclosed in German 1,062,059) has a similar herbicidal action.
The compound N-(3-tert-butylphenyl)-N',N'-dimethylurea disclosed in German Laid-Open Application DOS 2,436,108 has an intensive herbicidal action. However, it is tolerated to an in-sufficient extent by cereals. The compound M-(3-meth~lphenyl)-N'-methoxy-N'-methylurea disclosed in German Laid-Open Appllcatlon ~106~530 ` O.Z. 32,768 DOS 1,905,598 has on average a somewhat weaker herbicidal action, combined with a somewhat more favorable but verJ mar~inal selectivity in cereals.
We have no~r found3 surprisingly, that methoxymethylurea derivatives of the formula , ~ 3 (I
\ OCH3 ~here R denotes branched alkyl of 4 or 5 carbon atoms (e.g , isobutyl, sec-butyl, tert-butyl, l,l-~imethylprop~l, l-ethylpropyl, l-meth~lbutyl, 2,2-dimethylpropyl, 2-methylbutyl or 3-methylbutyl), have a very good herbicidal action on unwanted monocot~Jledonous and dicotyledonous (grassy and broadleaved) plant3, includin~ Galium aparine, and are excellently tolerated by cereals, especially winter cereals (rye, wheat, barley), upon both pre-emergence and postemergence applicat on.
The compounds according to the invention are .,ovel 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 me'hods wlth the aid of phosgene into the corresponding ar~Jl isocyanate of t'ne 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 E

llQ~530 O.Z. 32,768 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 sul~ate.

~ H COCl2 ~ ~-C=O II7 H_ R II R III

~ NH-C-~,7H (C~3)2S34 ~ ~ oCH3 R IV R

Instead of hydroxylamine or a salt thereof, it is also pos-sible to use N-methylhydroxylamine or O,N-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:

CH3 ~ NH-C-N

R II V R

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, 1954.

110~530 ~oute 1 is preferred, Example of a suItable aniline of the formula II .is m-tert~butylaniline (b~p. (0.01 mm)- 73C).

~ At 20 to 40C, 12.4 parts (by weight) of N-methoxy-N-methyl-carbamic acid chloride i5 dripped into a solution of 14.9 parts of m-tert-butylaniline and 10.1 parts of triethyla-mine 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-N'-methyl-urea; m.p. 82 -83 C.

///

Suitable application methods ~or the new active ingredients are incorporation into the soil, treatment of the soil sur~ace, 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 o~ 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 j and which were filled with a sandy loam containing .
~ 5 ~

O.Z. 32,768 about 1.5% humus. The seeds of the test plants (cf. Table 1) were sown shallow, and separately, according to species. For the pre-emergence 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, an~ sprayed through ~inely distributing no~les. 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 tc a height of 3 to 10 cm, depending on the growth shape, bePore being treated. The vessels were not covered after treatment. The pots were set up in the greenhouse. The experiments ~ere 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 applicatio~
rates in kg/ha of active ingredient, and the plants used for the tests. The scale used for assessment was O 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 l~as30 o.~. 32,768 therea~ter. 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 ~lora was made up o~ a wide variety o~ species, and was natural. The ~ubstances were emulsi~ied or dispersed in water as vehicle, and applied by means of a motor-drivn ~lot s~ray mounked on a tractor. Naturally occurring precipitation was suf~icient to ensure ~ermination and growth of the crop plants and weeds. 411 the experiments were run ~or several months. During this period, assessments on the O 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 cereal3 is also good. Compared with the prior art compounds used, the compounds according to the invention exhibit a much better control of broad-leaved 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.

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O.Z. 32,768 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:

_ ,S02 Rl R2 H ~ H and salts EI ~ Cl a~d~s-alts H ~ F and s.alts H ~ CH3 and salts N ~
N N,S02 'an-d--~s2lts H

>=~ ~ N-C-O-CH2-C--C-CH2Cl Cl ~ O

i C3X7 ~ N-C-S-CH2-CCl=CHCl i C3 7 s3a O.Z. 32,768 Rl-C-C-O-R2 .-Y O

Rl X Y R2 Cl-~-CX2- Cl ~T~ 3 ~C - N - H CH3 C2H5 O ~ , Cl Cl ~C - N - H CH3 CH3 ¢~Cl F

~C - ~ _ H CH3 i-C3H7 ~ C l Cl-~3-0-~-0 H CH3 -CH2-C\ t Cl-~)-O-~-O- H CH3 CH3 Cl O.Z. 32,768 N~N
J~ J~
R HI~ NHR

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C2H5 Cl -C t CH3 ) 2 CN
C2H5 Cl -cH-cH2-ocH~

C2H5 SCH3 tert. CI~Hg o H ~ N ~ CH

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3 H salts and esters H sec.C4Hg H salts and esters O.Z. 32,768 Rl ~X~

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Rl ~ R4 ~ and salts, esters Rl R2 R3 R4 Cl H Cl OCH3 Cl Cl ~ Cl Cl Cl Cl OCH3 Rl-O- CH- C-o-R3 n Rl R2 R3 Cl- ~ - H H salts, esters,amides Cl Cl- ~ - CH3 H salts~ esters, amides Cl Cl- ~ - H H salts, esters, amides 0.Z. 32,768 C1- ~ - CH~ H salts, esters, amides Cl Cl- ~ - H H salts, esters, amides Cl Cl- ~ - CH~ H salts, esters, amides Cl CH2-COOH and salts, esters b~ s ~o ?

and salts, esters HO COOH

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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 formsof application depend entirely on the pur-pose for which the agents are being used; in any case they should ensure a fine distribution of the active ingredient.

O,Z, 32,768 For the preparation of emulsions, pastes and oil dis-persion3 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 ben7ene, toluene, xylene, paraf-in, 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 con-centrates, pastes, oil dispersions or wettable po~ders by t 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 ~0 possible solvent or oil.
Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalene-sulfonic 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 ... . ~ . ~

O.Z. 32,768 glycol ethers, condensation products of sul~onated 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 nonyl-phenol, alkyiphenol polyglycol ethers, tributylphenol poly-glycol ethers, alkylaryl polyester alcohols, isotridecyl alcohols, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxy-propylene, lauryl alcohol polyglycol ether acetal, sorbitolesters, 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 gra-nules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicic acid, silica gels 9 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.

53C~

There m~y be added to the compositions or individual active ingredients oils o various t~pes r 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.

90 parts o~ weight of the compound from Example 1 is mixed with 10 parts by weight of N-methyl-~ -pyrrolidone. A
mixture is obtained which is suitable for application in the form of very fine drops.

3 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.

40 parts by weight of the compound from Example 1 is intimately mixed with 10 parts of the sodium salt of a phenol-sulfonic 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.

~ 25

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. An N-phenyl-N'-methyl-N'-methoxyurea derivative of the formula:

, where R denotes branched alkyl of 4 or 5 carbon atoms.

2. 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 of the formula:

, where R denotes branched alkyl of 4 or 5 carbon atoms.

3. N-(3-tert-butylphenyl)-N'-methoxy-N'-methylurea.

4. A process for controlling the growth of unwanted plants, which comprises applying N-(3-tert-butylphenyl)-N'-methoxy-N'-methylurea to the vegetation in an amount sufficient to prevent unwanted growth.