DE1643731A1 - Urea derivatives - Google Patents

Description

Badische Anilin- & Soda-Fabrik Ag1 643731

Our reference: O.Z. 25 344 Schs / Gn Ludwigshafen / Rhein, January 4th, 1968

Urea derivatives

The present invention relates to new urea derivatives and herbicides containing them.

It is known to use trisubstituted urea derivatives, e.g. 3- (4'-chlorophenyl) -1-methyl-1-methoxyurea, to use for weed control. Their compatibility with crops such as barley (Hordeum vulgare), wheat (Triticum sativum) and Rice (Oryza sativa), however, does not give satisfaction. Also disclosed in U.S. Patents 3,254,984 and 3,278,292 are substituted 3-phenyl-3-hydroxyureas, for example 3- (4'-chlorophenyl) -3-hydroxy-1-methylurea, known as herbicides.

It has been found that compounds of the formula

in which R ₁ and Rp are the same or different and are hydrogen or an alkyl group having 1 to 5 carbon atoms, R, is alkyl of 1 to 5 carbon atoms or the Isobutinyl- rest (Clk-CH-C ⁵ H), X is an oxygen atom or a Sulfur atom

768/67 _2-

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and Y and Y .. are identical or different and are hydrogen or represents a halogen atom such as chlorine or bromine ", and the salts thereof have a good herbicidal effect. Salts include in particular the salts of the alkali metals (sodium, potassium) or alkaline earth metals (magnesium, calcium) or the ammonium salts or the salts of organic amines (methylamine, ethylamine, dimethylamine, diethylamine, aminoethanol, Diethanolamine, trimethylamine). Some of these salts are soluble in water.

The compounds can, for example, by implementing the appropriate substituted phenylhydroxylamines with substituted isocyanates, isothiocyanates or carbamic acid chlorides getting produced.

To prepare the compounds in whose formula E ₁ denotes an alkyl radical, the corresponding hydroxyurea derivatives can, for example, be reacted with an alkylating agent.

The following test information is intended to facilitate the preparation of the inventive Explain connections.

a) 88.5 parts by weight of 3-trifluoromethylphenyl-hydroxylamine are dissolved in 300 parts by weight of toluene and at room temperature 28.5 parts by weight of methyl isocyanate are added with thorough stirring. The resulting precipitate is filtered off with suction Toluene washed and dried. You get 95 weight

parts 3- (3'-trifluoromethylphenyl) -3-hydroxy-1-methylurea off; Pp. 124 to 126 ⁰ C. -3-

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b) 46.3 parts by weight of 3- (3'-trifluoromethylphenyl) -3-hydroxy-1-methylurea are suspended in 150 parts by weight of water and 200 parts by weight of dioxane and at room temperature with good stirring with 13 parts by weight of sodium hydroxide dissolved in 50 parts by weight of water , solved. 37.8 parts by weight of dimethyl sulfate are added dropwise to the solution thus obtained at a temperature of 35 to 55 ° C. The mixture is then stirred for a further 2 hours at 50 ^° C., cooled and the solution is extracted with methylene chloride.

The crystals remaining after evaporation of the methylene chloride solution are recrystallized from cyclohexane. 40.2 parts by weight of 3- (3 ^f -trifluoromethylphenyl) -3-methoxy-1-methylurea are obtained; Pp. 76 to 78 ⁰ C.

The other compounds according to the invention can according to corresponding processes are produced.

As a starting material for the production of the compounds, for example, the following pheny! Hydroxylamines are imprinted, which in turn can be obtained from the corresponding nitrobenzenes by reductions:

3-trifluoromethylphenyl hydroxylamine

3-trifluoromethyl-4-chloropheny! Hydroxylamine and 2-chloro-5-trifluoromethylpheny / hydroxylamine.

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Preparation of 3-trifluoromethylpheny / hydroxylamine 22 parts by weight of ammonium chloride are dissolved in 260 parts by weight of water and 520 parts by weight of ethanol and 192 parts by weight of 3-trifluoromethylnitrobenzene are suspended in the solution thus obtained. The mixture is heated to 70 ⁰ O and puts it at a temperature of 70 to 80 ⁰ C with good stirring in portions with 172 parts by weight of zinc dust. After the addition has ended, the zinc salts are filtered off and the filtrate is freed from the solvent in vacuo. The remaining oil crystallizes. 160 parts by weight of 3-trifluoromethylphenylhydroxylamine are obtained; JPp. 48 to 50 ⁰ C.

As the compounds according to the invention, some will be mentioned below Substances listed:

3- (3'-trifluoromethylphenyl) -3-hydroxy-1-methyl urea; Mp 124-126 ° C

3- (3'-trifluoromethylphenyl) -3-methoxy-1-methylurea; Pp. 76 to 78 ° C

3- (3 ^! -Trifluoromethylphenyl) -3-hydroxy-1-methylthiourea; Pp. 133 to 135 C

3- (3'-TrifluoromethylphenylJ ^ -hydroxy-i-isopropylurea; pp. 116 to 117 ^° C.

3- (3'-trifluoromethylphenyl) -3-hydroxy-1,1-dimethylurea; ηψ = 1.5098.

The new compounds can be used as herbicides in the form of solutions, emulsions, suspensions or dusts will. The forms of application depend entirely on the intended use; they should be a fine one in any case Ensure distribution of the active substance. ~

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Come to the production of directly sprayable solutions Water, mineral oil fractions with a medium to high boiling point, such as kerosene or diesel oil, and coal tar oils as well Oils of vegetable or animal origin, as well as cyclic hydrocarbons such as tetrahydronaphthalene, and alkylated ones Naphthalenes into consideration.

Aqueous application forms can also be made from emulsion concentrates, Pastes or wettable powders (wettable powders) can be prepared by adding water. For the production of emulsions you can the substances as such or dissolved in a solvent, homogenized in water using wetting or dispersing agents will. But it can also consist of an active substance, emulsifying or dispersing agent and possibly a solvent Concentrates are prepared that are suitable for dilution with water.

Dusts can be produced by mixing or grinding together the active substances are produced with a solid carrier.

The addition of other biologically active ingredients such as fungicides, insecticides or other herbicidally active compounds, is possible. The herbicides can also be used as granules.

The following examples show the application of the new Active ingredients.

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example 1

In the greenhouse the plants were barley (Hordeum vulgare), Wheat (Triticum vulgare), rice (Oryza sativa), annual Bluegrass (Poa annua), chicken millet (Panicum crus galli), green millet (Setaria viridis), field mustard (Sinapis arvensis), small nettle (Urtica urens) and chickweed (Stellaria media) "at a height of 2 to 12 cm with 1.5 kg / ha of the active ingredients 3- (3'-trifluoromethylphenyl) -3-hydroxy-1-methylurea (i) and in comparison with 3- (4'-chlorophenyl) -3-hydroxy-1-methylurea (II) and 3- (4'-chlorophenyl) -1-methyl-1-methoxyurea (III) each dispersed with sodium lignosulfonate in 500 liters of water ever ha treated.

After 3 weeks it was found that the active ingredient I opposite II shows a stronger herbicidal action and, compared with III, is better tolerated by barley, wheat and rice.

The test result can be seen from the following table:

I. o-io Active ingredient III 0-10 II 30th barley 10 10 30th wheat 90-100 10 30th rice 90-100 10 90 annual bluegrass 70 90-100 Chicken millet 60-70

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- 7 - I. O.Z. Active ingredient 1643731 90-100 II 25 344 90-100 70 100 80 III green millet 90 80 90-100 Mustard 70-80 90-100 small nettle 100 Chickweed 90-100

0 = no effect
100 = total effect

Example 2

In greenhouse pots were filled diameter of 8 cm with loamy sand soil, and the seeds of maize (Zea mays), annual bluegrass (Poa annua), ITughafer (Avena fatua), wild mustard (Sinapis arvensis) _s small nettle (Urtica urens) sown and So prepared soil is treated with 3 kg / ha of 3- (3'-trifluoromethylphenyl) -3-hydroxy-1-methylurea (I) dispersed with sodium lignosulfonate in 500 liters of water per ha.

After 4 weeks it was found that the plants were annual bluegrass (Poa annua), ITugh oats (Avena fatua), field mustard (Sinapis arvensis), small stinging nettle (Urtica urens) were almost completely dead, while maize continued to grow without damage .

Biologically just as effective as substance I in Examples 1 and 2 are:

3- (3'-Trifluoromethylphenyl) -3-methoxy-1-methylurea 3- (3'-Trifluoromethyl-4 ^f -chlorophenyl) -3-hydroxy-1-methylurea

-S-109826/1359

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3- (3'-trifluoromethyl 1-4'-chlorophenyl) -3-methoxy-1-methyl urine off

3- (3'-trifluoromethylphenyl) -3-hydroxy-1,1-dimethylurea 3- (3'-trifluoromethylphenyl) -3-methoxy-1,1-dimethylurea 3- (3'-trifluoromethylphenyl) -3-hydroxy-1-isopropylurea

3_ (2'-chloro-5'-trifluoromethylphenyl) -3-hydroxy-i-methyl urine off

3- (3'-trifluoromethylphenyl) -3-hydroxy-1-methylthiourea.

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Claims (2)

- 9 - O.Z. 25 344 patent claims 1. Urea derivatives of the formula in which R- and R _{2 are} identical or different and are hydrogen or an alkyl radical with 1 to 5 carbon atoms, R, an alkyl radical with 1 "to 5 carbon atoms or the isobutinyl radical (CH ₅ -CH-CSCH), X an oxygen atom or a sulfur atom and Y and Y _{1 are the} same or different and represent hydrogen or a halogen atom, and their salts. 2. Herbicide containing a urea derivative, as in the Claim 1 is characterized. Aniline & Soda Factory in Baden 109826/1959