CS200247B2 - Herbicide and process for preparing effective compound - Google Patents

Description

The present invention relates to a herbicidal composition, the active ingredient of which is a urea derivative.

The present invention provides a herbicidal composition comprising, as an active ingredient, a compound of the formula X nhcn;

NHC-Rg

II o

(i) in which it denotes

R 8 is C 1 -C 6 alkoxy, C 1 -C 6 alkyl or hydrogen,

R 4 is furfuryl or C 1 -C 6 alkyl,

R 8 is C 6 -C 8 ethylcycloalkyl, pinonoyl, C 1-6 alkyl; C 1 -C 6 -halogenated, C 1 -C 6 -halogenated alkyl, C 1 -C 6 -halogenated alkyl or 2,4-dichlorophenoxymethyl-phenyl.

The compounds of formula I have both pre-emergence and post-emergence herbicidal activity.

A particularly preferred active ingredient is 1- (trans-tert-butylsceteaidophenyl) -3-methyl-3-methoxyurea of the formula

These active compounds are preferably prepared according to the invention by the compound of the formula II

NH,

NHC — Re II ⁵ 0 (II), wherein R R is as defined above, is reacted with a compound of formula III ^R 2? NiC-Cl (III),

in which

R ₂ and R have the above meanings, in the presence of a hydrogen halide acceptor or Rg represents where in the compound of the specimen, hydrogen, also a compound of formula IV

R @ 1 NCO, (IV),.

wherein R 1 is as defined above.

Several examples of the preparation of compounds of Formula I are given below.

Example!

Preparation of 1- (3 '-3-cyclopentylpropionamidophenyl) ethylurea

10.6 g of N-meta-amidophenyl-N'-ethylurea are dissolved in 100 cop of acetone containing

6.7 g of triethylamine and 10.6 g of 3-cyclopentylpropionyl chloride are added dropwise with stirring. The mixture was poured into water to crystallize the product. This was then filtered, washed with sodium hydroxide, hydrochloric acid solution and water until a neutral filtrate was obtained. The product is dried in a vacuum oven. 17.8 g of product, m.p. 1.97 DEG-200 DEG C. are obtained.

Example 2

Preparation of 1- (3 ^# -pinonoylamidofenyl) -3-ethyl-urea

10.8 g of N-meta-aminophenyl-1'-N'-ethylurea are dissolved in 100 cm @ 3 of acetone containing

6.7 g of triethylamine and 13.3 g of pinonoyl chloride are added dropwise with stirring. The reaction mixture is poured into water where the product crystallizes. This was filtered off, washed with sodium hydroxide and then dried overnight in a vacuum oven. The product is crystalline. 21.5 g of crude product are obtained, which is purified by washing with water until the mother liquor is basic. The filtrate is washed continuously with water until neutral and then with 5% hydrochloric acid and again with water until neutral. The product is dried in a vacuum oven. 16.4 g of product are obtained, m.p. 164-167 ° C.

OF

Example 3

Preparation of 1- (m-isobutyramidophenyl) -3-methyl-3-furfurylurea The title compound is prepared by reacting 12.3 g of 1-amino-phenyl-3-methyl-3-furfurylurea with 8.0 g of isobutyranhydride in the presence of a few drops of sulfuric acid. The mixture was stirred and then poured into water. The product is isolated. Yield: 14.1 g of the title compound, mp = 1.5467. Example 4

Preparation of 1- (m-2,4-dichlorophenoxyacetamidophenyl) -3-methyl-3-methoxyurea

For the preparation of this compound, 7.8 g of N-m-aminophenyl-N'-methyl-N'-methoxyurea is reacted in 100 .mu.m of acetone containing 4.5 g of triethylamine with 9.6 g of 2,4-dichloro-2-ol. phenoxyacetyl chloride. The product is isolated from acetone, filtered, washed with water and then dried. 13.0 g of the title compound are obtained, m.p. 139-143 ° C.

exampleS

Preparation of 1- (m-pivaloylamidophenyl) -3-methyl-3-methoxyurea

To prepare the compound, 11.7 g of N-m-aminophenyl-N'-methyl-N'-methoxyurea dissolved in 100 cm @ 3 of acetone containing 6.5 g of triethylamine are reacted with 7.3 g of pivaloyl chloride. The product is isolated from acetone, washed and dried. 11.2 g of the title compound are obtained, n-Q ° = 1.5463

Example 6

Preparation of 1- (m-pentafluoropropionamidophenyl) -3-methyl-3-methoxyurea

This compound is prepared by reacting 9.8 g of N-m-aminophenyl-N'-methyl-N'-methoxyurea dissolved in 100 cm 3 of acetone containing 5.5 g of triethylamine with 9.2 g of pentafluoropropionyl chloride bubbled into the solution. The product is isolated from acetone, washed and dried. 10.9 g of the title compound are obtained, m.p. 118-119 ° C.

Example 7

Preparation of 1- (m-tert-butylacetamidophenyl) -3-methyl-3-methoxyurea

9.7 g of 1- (m-aminophenyl) -3-methyl-3-methoxyurea in 100 cm @ 3 of acetone containing 5.5 g of triethylamine are reacted with 6.8 g of tert-butylacetyl chloride. The product is isolated by separation from acetone. 1.5.1 g of 1- (m-tert-butylacetamidophenyl) -3-methyl-3-methoxyurea are obtained, m.p. = 1.5452.

The following is a table of compounds that were prepared according to the procedures described. For identification and accurate labeling, the compounds were numbered.

Table I

Combination R, R, Re m.p.

and H ^C 2 ^K 5 CHnCHg-cyclopentyl 197 to 200 2 H ^C 2 ^H 5 CHgCHg-cyclohexyl 189 to 191 3 H ^C 2 ^H 5 pinonoyl 164 to 167 4 H CH _{3 2-CH3} -phenyl 159 to 160 5 H CH _n 3-CH ₃ -phenyl 195 to 197 6 H CH, 4-CH ₃ -phenyl 219 to 221 7 CH, ^CH 3 _2-CH3 -phenyl 129 to 132 8 • ch ₃ ch ₃ 3-CH ₃ -phenyl 144 to 147 9 ^CH 3 ch ₃ 4-CH ₃ -phenyl 173 to 175 10 och ₃ CH ₃ cci ₃ 148 to 150 11 OCH ₃ CH ₃ cf ₃ 140 12 och ₃ CH ₃ c ₂ f ₅ 118 to H9 13 OCH ₃ ^GH 3 c ₂ h ₅ 107 to 110 14 OCH ₃ ch ₃ t-C ^ Hg 1, 5463 15 Dec och ₃ ch ₃ CH 2 Cl 2 1, 5463 16 OCH ₃ ch ₃ C (CH ₃ ) ₂ C ₃ H. _f 1.5410 17 OCH ₃ ^CH 3 3-CH 3 -phenyl 1,5802 18 OCH ₃ ch ₃ 3-chlorophenyl 1.5943 19 Dec OCH ₃ CH ₃ 2,4-dichlorophenyl 1,5823 20 May 0CH, ch ₃ 2,4-dichlorophenyl-OCH ₂ 139 to 143 21 CH ₃ furfuryl cci 1,5908 22nd CH, furfuryl in ₅ 114 to 116 23 CH, furfuryl ^C 2 ^H 5 glassy substance 24 CH ₃ furfuryl ch (ch ₃ ) ₂ 1, 5467 25 CH ₃ furfuryl t-C ^ Hg 1.5613 26 ch ₃ furfuryl ch (ch ₃ ) c ₃ h ₇ 1.5548 27 Mar: CH ₃ furfuryl ch (c, h ₅ ) ₂ 129 to 131 28 CH ₃ furfuryl CÍCH ^C C 1.5570

The compounds of formula (I) have herbicidal activity and are useful for controlling the growth of various plant species. Their herbicidal activity was tested as follows:

Pre-emergence herbicide test

The day before the test, the seeds of seven different weed species were planted in individual rows using one species per row across the entire width of the box. Seeds of the blood-grass (Digitaria senguinalis / L / scop.), Gray grass (Setaria glauca / L / Beauv.), Hedgehogs (Echinochloa crusgalli / L./ Beauv.), And oat (Avena sativa / L./) were used. ), Amaranthus retroflexus (L./), Rush Mustard (Brassica juncea / L·./ Coss.) and Curly Dock (Rumex crispus /!,./). Enough seed was planted to germinate 20 to 50 seedlings in the row after application, depending on the size of the plants. After planting the areas were sprinkled. The spray solution was prepared by dissolving 50 mg ®

test compound in 3 cm solvent such as acetone containing 1% Twen 20-5200247 (polyoxyethylene sorbitan monolaurate). The following day, each box was sprayed with a solution containing 9.072 kg of test compound in 363.67 ± 2 l of solvent per 0.4 ha. Sprayers were used to spray the solution onto the soil surface. The boxes were placed in a greenhouse at 26.7 ° C and watered regularly. Two weeks later, the degree of weed control was determined by comparing the rate of germination and growth of each weed in the spray boxes with the weeds in several control boxes without the use of herbicide,

The evaluation system is as follows:

- - no significant damage (0 to 15% effect on growth) + '= slight damage (25 to 35% effect on growth) ♦ + = slight damage (55 to 65% effect on growth) ♦ + ♦ = severe damage or death (85 to 100% impact on growth)

The efficiency index is used to express the overall efficacy for all 7 weed species.

It is the sum of positive numbers, so the efficiency index 21 represents the complete destruction of all 7 weed species. The test results are shown in Table II.

Postemergence test

Seeds of 5 weed species, namely bloody dew, hedgehog corns, deaf oats, rush mustard and curly sorrel, and one crop plant, Phaseolus vulgaris, were planted as described above in the pre-emergence test. The boxes were placed in a greenhouse at 22.2 ° C to 29.4 ° C and watered daily. 10 to 14 days after planting, when the bean leaves of the bean were fully developed and the first shamrocks began to form, the plants were sprayed. The spray was prepared by dissolving 50 mg of the test compound in 5 cnP acetone containing 1% Tween 20 ® (polyoxy 3 ethylene sorbitan monolaurate) and then adding 5 cm of water. The solution was sprayed with a foliage sprayer. The spray concentration was 0.5% and its amount was approximately 22.44 kg / ha when all spraying of the plant and soil was captured, but with some loss of spraying the amount was estimated to be approximately 14 kg / ha.

Beans were used to determine defoliation and affect plant growth. A few days before the test, two or three bean plants were selected per box by cutting off excess weaker plants. The sprayed plants were placed back in the greenhouse and the leaves were not sprayed with water three days after the test. The soil was irrigated with a mild stream of water from the spray hose without wetting the leaves.

Assessment of damage was performed 15 days after the test. The rating system is the same as the preemergence test described above, where the marks (-), (♦), (++) and (♦♦♦) have been used for different assessments of damage and growth impact. Symptoms of damage have also been reported. The maximum potency index for totally influencing the growth of all 6 plant species used in the post-emergence test is 18, which is the sum of positive numbers. The efficiency indices are given in Table II.

Table II

Compound No. Preemergence

Postemergence

7

0 5 0 5 0 5 18 16 .12 14 12 . 14 15 Dec 18

Compound No.

.9

21 22

Preemergence, 5

2,

17 17 1

Postemergence

16 18 18 18 18 18 18

18 18 18 18 = 85 to 18 = 85 to

100% effect on growth of all 7 plant species at 100% effect on growth of all 6 plant species in preemergence test postemergence test

As can be seen from Table II, the compounds of formula I are highly effective pre-emergence and post-emergence herbicides. They compare to the most efficient known urea-based herbicides and, moreover, have a broad-leaf or grass type weed selectivity.

The herbicides according to the invention can be applied in different ways and in different concentrations. In practice, they are made with an inert carrier in a form suitable for application as powders, sprays, soaps and the like. They may be dispersed in water by a wetting agent or may be used in mixtures with organic liquids, in oil-in-water, water-in-oil emulsions, with or without the addition of a wetting, dispersing or emulsifying agent. The amount used depends on the nature of the seeds or plants whose growth is to be affected and ranges from about 1 to 5.6 kg / ha. A preferred method of application is a narrow strip close to the row culture.

The herbicides of the invention are applied to plants in a conventional manner. Powders and liquid mixtures can be applied to plants by spraying or spraying. They can also be applied from airplanes as a powder or spray because they are effective in very small doses.

To modify and control the growth of germinating seeds or growing seedlings, for example, powders and liquid mixtures are applied by conventional methods and are preferably incorporated into the soil to a depth of at least 1.27 cm below the surface. It is not necessary that the herbicides be mixed with the soil particles. They can only be applied by spraying or spraying on the soil surface. The herbicides of the invention can also be applied by adding to field irrigation water. This method allows the mixture to penetrate the soil simultaneously with the absorbed water. Powder mixtures, granular mixtures or liquid forms applied to the soil surface may be incorporated below the soil surface in a conventional manner, such as by planing, dragging or mixing.

The herbicidal compositions may also contain other ingredients, such as fertilizers, plant pest control agents and the like, used as adjuvants or in combination with any of the above-described compositions. Other herbicides useful in combination with Formula I include, for example, 2,4-dichlorophenoxyacetic acid, 2,4,5-trichlorophenoxyacetic acid, 2-methyl-4-chlorophenoxyacetic acid, and salts, esters and amides thereof; triazine derivatives such as 2,4-bis (3-methoxypropylamino) -6-methylthio-s-triazine, 2-chloro-4-ethylamino-6-isopropylamino-s-triazine and 2-ethylamino-4-isopropylamino-6-methylmercapto- 8-triazine; urea derivatives such as 3- (3,4-dichlorophenyl-1,1-dimethylurea and 3- (p-chlorophenyl) -1,1-dimethylurea and acetamides such as N, N-diallyl-alpha-chloroeetamide, N- (alpha-chloroacetyl) hexamethylenimine and Ν, Ν-diethyl-alpha-bromoacetamide and the like, benzoic acids such as 3-amino-2,5-dichlorobenzoic acid, thiocarbamates such as S-propyl dipropylthiocarbamate, S-ethyldipropylthiocarbamate, S-ethylcyclohexylethylthiocarbexate, S-ethyl-thiocarbexate, S-ethyl Ammonium nitrate, urea and superphosphates may be mentioned as artificial fertilizers to be used in combination with the active compounds of the invention, and other suitable admixtures are those in which the plant organism is rooted and grown, such as compost, manure. , humus, sand, and the like.

Claims (3)

A herbicidal composition, characterized in that it contains a compound of the formula (I) in which: R 8 is C 1 -C 6 alkoxy, C 1 -C 6 alkyl or hydrogen, R 8 is furfuryl or C 1 -C 6 alkyl, R 8 is C 6 -C 8 ethylcycloalkyl, pinonoyl, C 1 -C 10 alkyl, halogenated C 1 -C 6 alkyl, 2,4-dichlorophenoxymethyl, halogen-substituted phenyl or C 1 -C 6 alkyl. 2. The herbicidal composition of claim 1, wherein the active ingredient is 1- (m-tert-butylacetamidophenyl) -3-methyl-3-methoxyurea. 3. A process according to claim 1 wherein Rg, Rg and Rg are as defined in claim 1, characterized in that the compound of formula II is: NH ₂ NHC — Rg / II · o (XI), Wherein Rg, as defined above, is reacted with a compound of formula III ^H 2? NC-C1 (III), in which Rg and R3 are as defined above, in the presence of a hydrogen halide acceptor or, when Rg in the compound of formula I is hydrogen, also with a compound of formula R ₃ KCO (17), wherein R 6 is as defined above.