NL8601766A - PYRAZOLE COMPOUNDS AND THEIR USE AS HERBICIDES. - Google Patents

Description

> 4 λ 863062 / Ar / MW -1-

Pyrazole compounds and their use as herbicides.

The invention relates to compounds of the formula I of the formula sheet, wherein Rx is a hydrogen, halogen or methyl group, R is a hydrogen, halogen or lower alkyl group, R is a lower alkyl group optionally substituted by a halogen or methylsulfonyl group , an optionally substituted benzyl or phenyl group by a halogen atom or nitro group, a hydrogen atom, a lower alkyl group optionally substituted by a carboxyl group or a lower alkoxycarbonyl group, a lower alkenyl group, a lower alkynyl group, methylsulfonyl group or a benzyl group substituted by a halogen atom, hydrogen atom, halogen atom or alkyl group and Y represents an alkyl group, or X together with Y forms the group - (CH 2) 3 -, and W represents a halogen atom, a process for the preparation of this compound, herbicide compositions containing this compound and a method of controlling weeds by applying this e connection on the weeds or their place.

It is known that some pyrazole compounds have a herbicidal activity (see the compounds described in Japanese published patent application No. 52-91861 (1977)).

These known pyrazole compounds have never been effective in controlling weeds in rice paddies and highlands in small doses, and there is a demand for improved compounds.

In experiments of the present inventors with different pyrazole compounds, it has been found that the compounds of formula I of the formula sheet exhibit a particularly strong herbicidal activity and are also used in practice as herbicides because of their low phytotoxicity to productive crops. could be.

8601753 £. ν -2-

For example, the new pyrazole compounds of formula 1 of the formula sheet of the present invention can be prepared in the following ways:

By reduction of an N-substituted pyrazole compound of the formula 2 of the formula sheet, wherein 1 2 R, R, W, X and Y mean the formula 1 previously given.

JCclH

niches, for example, by the usual reduction of a nitro group to an amino group on an aromatic ring by means of sodium sulfide, iron powder, or a catalytic reduction, a compound 2 is obtained i 2 of the formula 3 of the formula sheet / wherein R, R, W, X and Y have the meanings given for formula II. For example, the above compound of formula 3 of the formula sheet can be obtained using iron-15 powder in the presence of a catalytic amount of an acid such as hydrochloric acid in an aqueous alcoholic solution, preferably at a temperature of 50-90 ° C for 1 -3 hours.

By reacting an N-substituted pyrazole compound of formula 3 of the formula sheet, wherein R 1, 2 R, W, X and Y have the meanings given for formula 2, with a sulfonic anhydride or sulfonyl halide with resp. formulas 4 and 4 'of the formula sheet, in which R "5 has the meanings given for formula 1 and Hal can represent a halogen atom / preferably at a temperature of 0-50 ° C, optionally in an inert solvent, if necessary in the presence of a suitable basic catalyst, a pyrazole compound of formula 1 of the formula sheet can be obtained.

By reacting an N-substituted pyrazole compound of the formula V in which R, R, R, W, X and Y, respectively. have the meanings given for formula 1, with a dialkyl sulfate or alkyl halide with formulas 6 and 6 'of the formula-35 sheet, wherein R 1 is optionally formed by a carboxyl group or. lower alkyl carboxylic acid ester substituted- lower alkyl group, a lower alkenyl group, a lower alkynyl group, a methyl sulfonyl group or an optionally halogen substituted benzyl group and Hal represents a 40 halogen atom, preferably at a temperature 8 δ 0 1 7 S δ «2 - 3- at 20-10 ° C, if necessary, in the presence of a suitable basic catalyst, optionally in an inert solvent, or alternatively by catalysis with a quaternary ammonium salt, preferably at a temperature of 20-100 ° C, with a suitable base in a water-inactive solvent, whereby a pyrazole compound of the formula 1 of the formula sheet, 12 3 4 in which R, R, R, R, W, X and Y have the aforementioned meanings, can be obtained.

By reacting a compound of formula 7 of 12 3 4 the formula sheet, wherein R, R, R, R, W, X and Y have the aforementioned meanings, with a halogenating agent, preferably at a temperature of 0- 80 ° C for 1-5 hours with the optional addition of an inert solvent such as chloroform, methylene chloride, acetic acid and N, N-dimethylformamide to give a pyrazole compound 13 4 of the formula 1, wherein R 7, R, R, W, 2 X and Y have the aforementioned meanings and R represents a halogen atom can be obtained. As the halogenating agent, a conventional reagent, preferably N-bromosuccinimide, N-chlorosuccinimide or sulfuryl chloride, can be used.

A compound 12 of formula II of the formula sheet, wherein R, R, W, X and 25 Y have the aforementioned meanings, is used as starting material, is obtained by an N-substituted pyrazolone of formula 8 of formula I, wherein R, R, X and Y have the aforementioned meanings to react with a halogenating agent, optionally with the addition of an inert solvent, such as chloroform, methylene chloride or toluene, preferably at a temperature of 60-180 ° C for 1- 15 hours under heating. The above reaction can be accelerated by the addition of a base such as dimethylformamide, pyridine or Ν, dial-dialkylaniline. As the halogenating agent, a conventional phosphorus halide, preferably phosphorus oxychloride or bromide, can be used.

By reaction of an N-substituted pyrazole "-12 compound of the formula (9), wherein R, R, 40 W, X and Y have the meanings given for formula 1, 8601736 [4] with a nitrating agent, such as concentrated nitric acid or fuming nitric acid, preferably at a temperature of -20 to -30 ° C in sulfuric acid to give a compound of formula 2 of the formula sheet wherein 125 W, X, Y, R and R are the aforementioned have meanings.

A compound of formula 12 of the formula sheet used as starting material in the above preparation methods is obtained by a compound of formula 10 of the formula sheet, wherein R is a lower alkyl group, and a substituted phenylhydrazine compound of formula 11 of the formula sheet, wherein R ^ represents a hydrogen atom or a nitro group to react in a suitable inert solvent, for example an aliphatic hydrocarbon such as methylene chloride, or an aromatic hydrocarbon such as toluene, an alcohol or an ether, preferably at 60-150 ° C for 30 minutes to Refluxed for 30 hours.

In the above reaction, if necessary, the reaction can be completed under milder conditions, for example at 5 ° C to the boiling temperature, by adding an appropriate base, for example triethyl amine, sodium hydroxide or sodium alkoxide.

A substituted phenylhydrazine compound of formula 11 of the formula sheet can be obtained by diazotizing a substituted aniline compound of 1 2 formula 13 of the formula sheet, wherein R and R have the aforementioned meanings, with sodium nitrite, and reducing the diazonium salt thus obtained with a reducing agent such as stannous chloride or sodium hydrogen-30 sulfite.

A compound of formula 15 of the formula sheet, wherein X represents a halogen atom, Y, W, R, R and R have the aforementioned meanings and R1 represents a hydrogen atom, nitro group or S09R8 -n '.

V

8 where R and R are lower alkyl groups can be obtained by halogenation of a compound of 12 7

40 formula 14 of the formula sheet, wherein Y, W, R, R and R.

8501756 have the aforementioned meanings, in acetic acid or an inert solvent such as chloroform, etc., preferably at 0-30dC, using a halogenating agent such as chlorine or bromine.

As the basic catalyst which can be used in the process of the present invention, there can be mentioned triethylamine, tributylamine, pyridine, N-methylmorpholine, N, N-diethylaniline, N, N-dimethylaniline, potassium and sodium carbonates.

As an inert solvent to be used according to the process of the invention, an aromatic hydrocarbon such as benzene, toluene and xylene and its halogen compounds such as chlorobenzene, an aliphatic hydrocarbon such as n-hexane, n-heptane and petroleum ether, a cycloaliphatic hydrocarbon such as cyclohexane, a halogenated aliphatic hydrocarbon such as chloroform, carbon tetrachloride and tetrachlorethylene, an ether such as ethyl ether, tetrahydrofuran or dioxane, an ester such as ethyl acetate, an amide such as dimethylformamide and water.

According to the present invention, the halogen atom can be a chlorine, bromine or fluorine atom. and can be mentioned as the lower alkyl group the methyl, ethyl, n and isopropyl groups. Furthermore, as halogen- or nitro-substituted phenyl groups, the p-nitro-phenyl, m-nitrophenyl, p-chlorophenyl, m-chlorophenyl and 2-chloro-4-nitrophenyl groups can be mentioned as the lower alkyl carboxylic acid ester or acidic carboxylic acid ester substituted lower alkyl group -CH 2 COOCH 2, -CH 2 COOC 2 H 5, etc. As the lower alkenyl group CH 1 -CH 1 -CHsC 1 and -C 1 -CsCf 1, and as the lower alkynyl group -C 1 ^ CsCH 1 can be mentioned.

The present compounds may be referred to as the preferred compounds represented by the following groups (A) and (B): (A): a compound of formula 1 of the formula sheet, 1 - 2 'wherein R is a fluorine or chlorine atom, R is a chlorine atom 3 4 or methyl group, R a lower alkyl group, R a methyl,

40 ethyl, carboxymethyl or methoxycarbonylmethyl group, X

8601783 2 -6- represents a chlorine atom and Y represents a methyl group, or X together with Y forms the group - (CH ^) ^ -, and W is a chlorine atom.

(B): A compound of formula 1, wherein a fluorine or chlorine atom or a methyl group, R is a chlorine or bromine atom or a methyl group, R is the group -SO ^ CF ^, R is a hydrogen atom, and X represents a methyl group or X together with Y forms the group. More preferred compounds are those of formula 1 1 2 10 of the formula sheet, wherein R is a fluorine atom, R a 3 4 chlorine atom, R a methyl or ethyl group, R a methyl, carboxymethyl or methoxycarbonylmethyl group, X a chlorine atom and Y represents a methyl group or X together with Y forms the group and W is a chlorine atom, and the most preferred compounds are the compounds of formulas 16 to 22 of the formula sheet.

When using the compound of the present invention to prepare a herbicidal composition, they can be used to enhance or stabilize the effect in the form of powders, granules, micrograins, emulsifiable concentrates, wettable powders, and fluids suspension concentrates by mixing them with additives according to a conventional agricultural chemical method.

The different compositions can be used as such or after dilution with water to a suitable concentration.

As additives can be mentioned carriers (diluents) and other additives, for example thickeners, emulsifiers, wetting agents, dispersants, binders and disintegrators.

As a liquid carrier, aromatic hydrocarbons such as toluene, xylene and methylnaphthalene, aliphatic hydrocarbons such as cyclohexane, ligroin and kerosene, alkanols such as methanol, butanol and glycol, ketones such as acetone, amides such as dimethylformamide, sulfoxide * such as dimethyl sulfoxide, animal and vegetable oils, fatty acids and esters thereof. As solid drains, clay, kaolin, talc, diatomaceous earth, silicon can be used.

dioxide, calcium carbonate, mcmtmorilonite, bentonite, feldspar, quartz, aluminum oxide and sawdust. I

As an emulsifier or dispersant it is commonly used

A surfactant is used, for example, an anionic surfactant such as sodium high alkyl sulfate, stearyl trimethyl ammonium chloride,

polyoxyethylene alkyl phenyl ether and lauryl betaine, a cation

nic surfactant, and non-ionic surfactant I

10 surfactant or an amphoteric surfactant I

agent. As thickener, for example, polyoxy-I

ethylene nonyl phenyl ether and polyoxyethylene lauryl ether, and the wetting agents mentioned are, for example, dialkyl sulfosuccinate and polyoxyethylene nonyl phenyl ether. As the BHD-15 agent, carboxymethyl cellulose and polyvinyl alcohol I.

and as a disintegrator sodium ligrolnesulfonate and the cal-I

cium salt of carboxymethyl cellulose.

Any of the above herbicide compositions can be used not only as such, but also in combination with 20 fungicides, insecticides, acaricides, nematocides, plants.

growth regulators or soil improvers I.

be applied. The herbicide composition I

according to the present invention can be used in a mixture with fertilizers and other herbicides.

The content of the active compound in the herbicidal composition of the present invention depends on the type and form of the composition, the mode of application and other conditions, and the content of the present compounds is usually in a range from 0.1-95 wt.%, preferably from 0.5-50 wt. Si.

In weed control, the amount in which the herbicide composition is applied depends on the compound used in the herbicide composition and the areas to which the herbicide composition is applied, but is generally 0.1 g, preferably 20 g of one of the present compounds per are (1 are = 100 m) of the area.

The compounds of the present invention show excellent herbicidal activity in a low concentration relative to arrowhead, rushes and 8601730 4 * -8-mizugayatsuri in rice fields with very low phytotoxicity to rice and also show a excellent activity in low concentration on millet, foxtail, wild amaranth and chenopodium-5 album with little toxicity to the productive crops such as corn, soybeans and highland cotton.

The present invention is further illustrated by the following examples.

Example I: 10 1- (3-Trifluoromethylsulfonylamino-4-chlorophenyl) - 3,4-tetramethylene-5-chloropyrazole (compound

No. 3):

1.5 g (0.0053 mol) of 1- (3-amino-4-chlorophenyl) -3,4-tetramethylene-5-chloro-15-pyrazole (preparation No. 6) are dissolved in methylene chloride and 1.7 g (0.0060 mol) trifluoromethanesulfonic anhydride at -5 to 0 ° C and then 0.6 g (0.0059 mol) triethylamine to the solution.

After stirring the solution at the same temperature for 2 hours, the entire solution is poured into water and the dichloromethane layer is extracted with a 5% aqueous sodium hydroxide solution. The basic extracts are acidified with hydrochloric acid and extracted with ethyl acetate. 1.1 g of yellow crystals are obtained by washing the ethyl acetate layer with water, drying and concentrating. Yields 50%. Melting point: 180-184 ° C.

Basic analysis ^ 4 ^ 2 ^ 2 ^ 3 ^ 3 ^ 2 ^ (414.25)

Calculated C: 40.59 H: 2.93 N: 10.15 Found C: 40.15 H: 2.90 N: 10.18 Example II: 30 L- (2-fluoro-4-chloro-5-trifluoromethanesulfonyl) - aminophenyl) -3,4-tetramethylene-5-chloropyrazole (compound No. 7):

3.5 g (0.012 mol) of 1- (2-fluoro-4-chloro-5-aminophenyl) -3,4-tetramethylene-5-chloropyrazole are dissolved in 20 ml of ethylene chloride and after cooling of the solution Add 1.7 ml (0.12 mole) of triethylamine with ice to the solution dropwise with 2.1 ml (0.12 mole) of trifluoromethanesulfonic anhydride. After stirring for 1 hour, the reaction mixture is poured into water and extracted with ethyl acetate. After 40 washings with water and concentration, the extract is separated 860 1 7 3 6 * -9-, purified in a silica gel column and 3.9 g of the desired product are obtained in the form of yellow crystals. Yield 75¾. Melting point 199-202 ° C.

Elemental Analysis C 14 H 14 Cl 2 E 2 N 3 O 2 • 1 Calculated C: 38.90 H: 2.57 N: 9.72 Found C: 38.95 H: 2.65 N: 9.76 Example III: 1- (4-Chlorine -2-fluoro-5-methanesulfonylaminophenyl) - 3,4-tetramethylene-5-chloropyrazole (Compound 10 No. 16):

2 g of 1- (5-amino-4-chloro-2-fluoro-phenyl) -3,4-tetramethylene-5-chloropyrazole are mixed with 5 ml of pyridine and after cooling to 0 ° C, 0.86 g of methanesulfonyl chloride are added dropwise with stirring .

After stirring for 2 hours, the reaction mixture is poured into water, extracted with ethyl acetate and washed with dilute hydrochloric acid. After further washing with a dilute aqueous sodium bicarbonate solution and ice water, the extract is dried over anhydrous sodium sulfate and recrystallized in a mixed solvent of n-hexane and ethyl acetate to give 2.0 g of white crystals, m.p. 175-176 ° C. obtains. The yield is 80¾.

Elemental analysis: C14HHC12W2S1 Calculated: C: 44.46 H: 3.73 N: 11.11 Found: C: 44.51 H: 3.69 N: 11.30 Example 4: 1- [4-chloro-2 -fluoro-5- (N-methyl-N-methanesulfonyl) aminophenyl-3,4-tetramethylene-5-chloro-pyrazole (compound No. 14).

1.6 g of 1- (4-chloro-2-fluoro-5-methanesulfonylaminophenyl) -3,4-tetramethylene-5-chloropyrazole (compound No. 16) are dissolved in 40 ml of acetonitrile, 0.6 g of dimethyl sulfate and 0.64 g of potassium carbonate and stirring under reflux for 3 hours. After cooling, the reaction mixture is poured into water, extracted with ethyl acetate and watered with water until neutral. After concentration, separation and purification by chromatography on a silica gel column, 1.3 g of white crystals with a melting point of 78-81 ° C are obtained. Yield 85.5¾.

40 Basic analysis: CHCIFNOS15 16 2 1 3 2 1 8601703 f -10-

Calculated: C 45.93 H: 4.11 N: 10.71 Found: C: 46.04 H: 4.06 N: 10.82 Example 5: 1- [4-chloro-2-fluoro-5- ( N-eth.ylsulfonyl-N-metho-5-xycarbonylmethyl) aminophenyl] -3,4-tetramethylene-5-chloropyrazole (compound No. 35):

3.8 g of 1- (4-chloro-2-fluoro-5-ethanesulfonylaminophenyl) -3,4-tetramethylene-5-chloropyrazole (compound No. 19) are dissolved in 50 ml of acetonitrile and 1.8 g are added. 10 methyl methyl bromoacetate and 1.7 g potassium carbonate. After stirring under reflux for 3 hours, cooling and pouring into water, the reaction mixture is extracted with ethyl acetate, washed with water until neutral, concentrated, isolated and purified with silica gel column chromatography to obtain 3.2 g of white crystals with a melting point of 134.5-135.5 ° C. Yield 71¾.

Basic analysis: ^ 20 ^ 2 ^ 1 ^ 3 ^ 4 ^ 1

Calculated: C 46.56 H: 4.34 N: 9.05 Found: C 46.72 H: 4.45 N: 9.10 Example 6: 1- [4-Chloro-2-fluoro-5- ( N-propargyl-N-methane-sulfonyl) -aminophenyl] -3,4-tetramethylene-5-chloro-pyrazole (compound No. 29).

1.9 g of 1- (4-chloro-2-fluoro-5-methanesulphonylaminophenyl) -3,4-tetramethylene are dissolved in 50 ml of acetonitrile. 1.3 g of propargyl bromide and 1.5 g of potassium carbonate are added and, after stirring under reflux for 4 hours, the reaction mixture is cooled, poured into water and extracted with ethyl acetate. The extract is washed with water until neutral, concentrated and after separation and purification by silica gel column chromatography, 1.7 g of white crystals, m.p. 136-137 ° C are obtained. Yield 81¾.

Elemental Analysis: ^ 7 ^ 16 ^ 2 ^ 1 ^ 3 ^ 2 ^ 1 35 Calculated: C: 49.05 H: 3.87 N: 10.09 Found: C: 48.96 H: 3.74 N: 10.18 Example 7: 1- [4-Chloro-2-fluoro-5- (N, N-dimethanesulfonyl) -aminophenyl] -3-methyl-4,5-dichloropyrazole (Compound No. 24).

-11- * *

2.0 g of 1- (5-amino-4-chloro-2-fluorophenyl) -3-methyl-4,5-dichloropyrazole are dissolved in 30 ml of methylene chloride and 1.7 g of methanesulfonyl chloride are added dropwise. While further adding 2 ml of triethylamine, the reaction mixture is stirred at room temperature for 3 hours, poured into water, extracted with ethyl acetate and washed with water. The concentrated product is isolated and purified by silica gel column chromatography, and 1.7 g of light brown crystals having a melting point of 190-10 192 ° C are obtained. Yield 65.4%.

Elemental analysis: ^ 2 ^ 11 ^ 2 ^ 1 ^ 3 ^ 4 ^ 2 Calculated: C: 31.98 H: 2.46 N: 9.32 Found: C: 31.90 H: 2.53 N: 9, 44 Example 8: 15 1- [4-Chloro-2-fluoro-5- (N-methyl-N-methanesulfonyl) -aminophenyl] -3,4-tetramethylene-5-chloropyrazole (Compound No. 14) .

3 g of 1- [2-fluoro-5- (N-methyl-N-methane-sulfonamino) -phenyl] -3,4-tetramethylene-5-chloropyrazole, 1.3 g of sulfuryl chloride and 30 ml of carbon tetrachloride are mixed and stirred 6 hours at 70 ° C. The mixture is poured into water and washed with a dilute aqueous sodium bicarbonate solution and then with water. The product is dried, concentrated and recrystallized from a solvent mixture of 25 n-hexane and ethyl acetate to give 2.8 g of white crystals, m.p. 78-81 ° C. Yield 85%.

Basic analysis: ^ 25 ^^^ 5 ^^ 2 ^ 1 ^ 302 ^ 1 Calculated: C: 45.92 H: 4.12 N: 10.71 Found: C: 45.99 H: 4.11 N: 10 .69 30 Preparation 1:

Preparation of 1- (4-Chloro-2-fluorophenyl) -3-methyl-5-chloro-pyrazole:

21.8 g (0.136 mol) of 4-chloro-2-fluoro-phenylhydrazine and 18.5 g (0.142 mol) of ethyl 3-oxobutanoate 35 are dissolved in toluene, the solution is refluxed and concentrated. A small amount of ether is added to the solution and the precipitated crystals are filtered to obtain 26.1 g of 1- (4-chloro-2-fluorophenyl) -2H-3-methyl-5-pyrazolone in 85% yield. .

To the obtained red crystals 15.3 g (0.126 8601768 -12-mol) of N, N-dimethylaniline and 19.4 g (0.126 mol) of phosphorus oxychloride are added and the mixture is stirred for 5 hours after heating to 130 ° C. The reaction mixture is poured into ice water and extracted with chloroform. The chloroform layer was washed with a dilute hydrochloric acid solution and then with water. The solid obtained by concentrating the extract was purified by column chromatography to obtain 15.0 g of 1- (4-chloro-2-fluorophenyl) -3-methyl-5-chloropyrazole in the form of pale yellow crystals, m.p. 95-97 ° C in a yield of 53¾.

Preparation 2:

Preparation of 1- (4-chloro-2-fluoro-5-nitrophenyl) -3-methyl-4-bromo-5-chloropyrazole:

To a solution of 12.5 g (0.043 mol) 1-15 (4-chloro-2-fluoro-5-nitrophenyl) -3-methyl-5-chloropyrazole in a mixed solvent of 100 ml chloroform and 100 ml acetic acid is added 3.9 g (0.047 mol) of sodium acetate and then 7.2 g (0.045 mol) of bromine at 10 ° C.

After stirring at the same temperature for 2 hours, the reaction mixture is poured into ice water and the chloroform layer is separated. The chloroform layer is washed with an aqueous sodium bicarbonate solution and water and concentrated to give 13.0 g of 1- (4-chloro-2-fluoro-5-nitrophenyl) -3-methyl-4-bromo-5-chloropyrazole. light yellow crystals with a melting point of 135-137 ° C in 82% yield.

Preparation 3:

Preparation of 1- (4-chloro-2-fluoro-5-nitrophenyl) - 3,4-tetramethylene-5-chloropyrazole: 8.7 g (0.0305 mol) 1- (4-chloro-2-) are added fluorophenyl) -3,4-tetramethylene-5-chloropyrazole to 20 ml concentrated sulfuric acid and add 1.64 ml (0.335 mol) fuming nitric acid (d = 1.5, 86 wt%) dropwise with cooling. After stirring for a short time, the reaction mixture is poured into a large amount of water and, after extraction with ethyl acetate, the extract is separated and the extract is purified by silica gel column chromatography, yielding 8.2 g of the product in the form of brown crystals with a mp 108-111 ° C, a yield 40 8601753 »τ -13- of 82¾.

Preparation 4:

Preparation of 1- (4-Chloro-3-nitrophenyl) -3,4-tetramethylene-5-chloropyrazole: 9.5 g (0.056 mol) of ethyl 2-oxocyclohexanoate and 7.9 g (0.055 mol) are dissolved ) 4-chlorophenylhydrazine in 50 ml of xylene, reflux the solution for 3 hours and filter off the crystals formed by concentration of the mixture to give 12.8 g of 1- (4-chloro-10-phenyl) -2H- 3,4-tetramethylene-5-pyrazolone.

To the whole amount of the crystals obtained, 8.7 g of phosphorus oxychloride and 6.9 g of N, N-dimethylaniline are added, stirred at 130 ° C for 5 hours, pour the reaction mixture into ice water and extract with chloroform.

The chloroform layer is dissolved with a dilute hydrochloric acid solution and water and the solid obtained by concentration is purified by column chromatography, adding 10 g of 1- (4-chlorophenyl) -3,4-tetramethylene-5-chloropyrazole in the form of pale yellow crystals in a yield of 20 73¾.

6.0 g (0.022 mol) of the 1- (4-chlorophenyl) -3,4-tetramethylene-5-chloropyrazole thus obtained are dissolved in 20 ml of concentrated sulfuric acid and the mixture is added at -5 to 0 ° C. 3 g of concentrated nitric acid (94¾).

After stirring at the same temperature for 2 hours, the reaction mixture is poured into ice water, neutralized with NaHCO 2 and extracted with ethyl acetate. The concentrate is purified by column chromatography and 5.3 g of the desired product are obtained in the form of yellow crystals with a melting point of 94-97 ° C in a yield of 76¾.

Preparation 5;

Preparation of 1- (5-amino-4-chloro-2-fluorophenyl) -3-methyl-4-bromo-5-chloropyrazole:

12.5 g (0.034 mol) of 1- (4-chloro-2-35 fluoro-5-nitrophenyl) -3-methyl-4-bromo-5-chloropyrazole (preparation 2) are added to a solution of 13.6 g of iron powder in 44 ml of ethanol. 20 ml of water and 0.2 ml of hydrochloric acid are added with stirring at 70-75 ° C. After stirring for 2 hours at 75 ° C, the reaction mixture is filtered, 40 cold water is added to the filtrate and extracted with ethyl acetate. Men 8-30 1 7 68

-V

The ester layer was washed with water, concentrated and purified by column chromatography to obtain 11.0 g of brown crystals, m.p. 113-116 ° C, in a yield of 96 °.

5 Preparation 6:

Preparation of 1- (3-amino-4-chlorophenyl) -3,4-tetramethylene-5-chloropyrazole:

4.5 g (0.014 mol) of 1- (4-chloro-3-nitro-phenyl) -3,4-tetramethylene-5-chloropyrazole (preparation 5) at 70-75 ° C are added with stirring to a solution of 5.8 g of iron powder in 20 ml of ethanol, 9 ml of water and 0.1 ml of hydrochloric acid. After stirring for 2 hours at 75 ° C, the reaction mixture is filtered, cold water is added to the filtrate and extracted with ethyl acetate. The ester layer is washed with water, concentrated and purified by column chromatography to obtain 3.2 g of brown crystals with a melting point of 87 DEG-89 DEG C. in a yield of 79 DEG.

The compounds according to the invention represented by the formula 1 of the formula sheet are summarized in the following table 1: 8S01736 -15- c 0 ίΗ c <-l c C ω ra ® ω c + J '!

^ -h 0 ra '"J

.yi — t ra 1 "<-η -p ra ra J £" -i ra ή yy 'p tn -π t. ra ra ”0 tl j« c - · ^ - -u J * 0 • π 0 ^ cn “3 0 C 4J -.

4J -π 0 x: ** 4J 3 o f • H tl 0 Ή * 3 _q C7i —i = = = - yy- -o ra <—f

XI

0 CJ o <- * (Λ CJ O o

- <N Ω CJ O CJ O CJ CJ CM O CJ U

EpO O O i — 10 O O O O O

fc »r *. csl Mt <f K \ M3 CM CM M3 ** - yy ... iiiii I i 1 1 1 4J 'o "c iA C3C3C0i-lfAO'0 \ ΡΛ (Λ 0) e 3 n \ 0 \ CO (Ά VO O 'O' O 'CO f'- X ra Q 1-1 r- * -1 Ή ^' '-l- ^ 1-1 ^ c ra _____> __------------ ---- * <r cc 0 3- = = = = = = = = = i — l 3 __.____- ε ------- u ^ 1—1 O Q-

^ IA

- * u. _ 0 -U CJ = - = = = = X3 0 __ ra ____________ ΙΟ ΙΛ

0 ΡΛ (Α ΓΑ X

CMX ^ i-l X X CMr-l f-l

CqTcj CJ CJ CJ CJ CJ CJ X CJ = • rt o _____ C ---------- 1 —'--- Ά ΓΑ ΓΛ

-Ω r-i X X

ti ££ CJ u. X CJ X X U- X U. = 0 3 = ________ F — i 30 = = = = = = = = ___ 2_

--- i Λ i _T

<t x <f S S

CJ ^ CJ CJ

> - CM CM ----.

—— + X —- X

CJ 1A CJ

___ x w ^ xi cj I = = = = = __ ^ __ m 1 o c z «Η n σ

U C Q

0-1-1 U

> -0, -H CM ΓΑ <f Ά M3 Γ- CO 0 \ i-H | £ 601728

I i V

-16- I C lie I — I 0 I — i <—I o

CO I — I CO CO — I

4J (—i -J Ρ P

CO CD C 03 C 03 ta -H -J 0 P 0 P 4-) p 03 • —l P P P 0

JC Ρ I — I JC P JC P

p CD 03 P

0 .y + j 0 -p ω pc

c 03 C 03 C

· Η 0 Ρ · Η · Η Ρ 0 Ό 3 'ι — I Ρ 3 Ρ 3 ι — i • Η Ρ 0 PC PPCP0 ρ - xj σι ϋ J3 σι Ρ pi + J 0 -Ρ 0 -Ρ -Ρ 0JTJZ - υ χ: -μ χ: _ .c + J 0CÜ -Ρ OC-P ϋ ^ Ο • Ρ · Ρ 0 · Ρ · Ρ · Ρ 0 · Ρ · Ρ · Ρ X rprpip = 3 = = Ρ Ρ S Ρ ^ Ρ ΙΑ

Μ Ο CJ CJ

C ο U Ο CJ

IACJCPO rPCJO CPU

I ~ Ο Ο rp I — ΙΟ O O O CJ

ρ · ~ Ρ Μ CM CO Ρ M3 -Ο- Α M3 Ο ρ Ρ 1 I I I I 1 I I I ΙΑ

0C O Ο γΡ C0 σν ΙΑ A O ’<) · I

Ε3α ΙΑ <ί Ρ- Ο Α Ο · A3 Ο 03 Q. CM rp Ρ Ρ Ρ Ρ Ρ Ρ Ό * ρ αη

ΑΧ A

• I X Al X

® 0 £ X X CJ = CJ X = = - CJ

XI

0 ______ — __-______ "ρ - 'σι a a p ΑΧ ΑΙ ΧΑΧΑ

L Α Ll. Al X CM X Al X

^ o; cj ο = cj = = acjcju ρ _____ 0 ---..------- 3 »

CM Ρ P

cea3u: = = = = = = =

P

ecu .:::: = - XXU_

i — H

3 O = = = = = = __ = __ = __ = _

a

1 X: I A

<j CJ -sf X

> - / - CJ

CM CM -

--- -J- - · ........ "X

O CJ

-R p w P

X I CJ - 1 :::: = CJ

♦ I a ex

• P

x σι ρ c

0-PP CM A <f A M3 P CO ON O

> 10 ρ ρ ρ P ρ P p P P CM

86017ÖÖ -17- i te- c -I -10 ω co ra -P + J rl 'H _ m co co c ra c .η -π -p ra -p ra h CO p co -t co -c ra * h - «, H η * ti ra p ra 0 cn ra - ¥ -p -pcc co co v -η · π ra -p ra -η • rj 3 ra □ -1 P ^ • η ρ ra tira ^ ® - tx cn -Q σι σ cjjj-u 4J-ura jjra

ra ï j = jc - £ =. +> j: -P

4JOCÜ ÜCÜ-P ü + j

• π · η ra ή · η ra ή · η · Η - ^ J

3 1-1-11-1 => —I * —i i— · 3 - s ~ ia σι "P 2 CJ o .AU -C uuuouoo.

ίο οο σαοαο Γ ^ ΐΑ 4JfA COO CM CA MT CM MD '' —c -pi com iii I Xl5o ra c cm ra ioo ca o £ m α εσαο —i ca σ \ ca m cr \ m ή 1-1 co α p cn <r__> h__cm__d __: 2__zi .____—-- —— u CS) CA 1 "2 5" «?.

CM X = = 1 CM

-I O 2 S

ra cc x = = __ cn ______ o-i—— 1 -.-— x * "" "----- ra ^ o -η + j. c z u u Γ m = N € x". φ φ φ £ n. . .

XUUU = Γ f IO-- σ ____- ψ-Λ ————— ""

O

P ^ fA

O CM —f X. = Π> QC U = = = - UUUCJ-

IA

-Η 'X

XÜ- = = = = X U.CJ Cx. = _ r — 1 _ 3 cj = = __- = = = = = __ "_" ^

1 X = = I

> Mf CJ ^ _sfr

Ίμ ___ CM

- X X

u ° s_4 —i P - 'x 1 = u = CÜ I = = = = I o c z

<P

x cn P c ra ή —i cm ca si m o r-co ολ o

> -u CM CM CM CM CM CM CM CM CM CA

8601735 -18-r-1 ra

-P

c co c c ra · η ra ra pp p i — i ra i — t

r — I r — I · Η I — I

ra ra i — i co

4y ra -p o -P

co c co co JC · Η Ή · Η ra · Η Ά p 3 P 1—1 p • h je ρ jc ra jé

rH J3 CT

p ra -p ra -P ra ra -P x -P x -p

+ j + j o c -P ra -P

• H * r1 Ή (ΰ * H * P, r "l X 3 = r-1r43 = = = = <" I 3

YOU

LA O

N Q LA

C «CJ CJ

CJ CJ CJ LA CJ CJ O O

i cjoo o loo -Hirso

-p ·· »O CM LA A LA CT \ <f O LA IA

A -P CO M3 I I «I I Ή Γ" 'I

raci ι-ra- cm -ra · co cm i la oo E 3 m3 oo r- ~ a a> -ι σ \ «cm

CO Q. CO ΙΛ 1—1 Ή i — 1 CM CM Os <—1> —I

ΓΛ <—i 3: ^ cj u x • η J. a a w fyv} a o r "IUJ cj cj

X CM CS

IA 'cm XX A

Sf CJ X CJ CJ X

a: i. t x = I ixcj = x r — 1 ”" ï ύ ra ^

-P / Y I LA CJ

ίγ-γ | is x ia cm

C A [111 X CM X X A

ra ax γΧ u cj o cj x> ca u ~ Ti i = i = i cj σ A »'<-'..... -......... 1 - -...... -.......... "" .........

O

> A

P CM ι-H i-I X

ra ce cj = = = = = Lu cj s cj

Os

i — I

X Lu = = = = = = X Lu X

r— (3 CJ - - = = = = = = = - |> · <f - *

CM

-— X

CJ

sp X t = = = = = = = = __ =

I o C X • H

J3 CT P C

ra-Hr-H CM A -Cf A M3 A »CO Ol O

3> TJ A A A A A A A A A

8801736 -19-

c c S

© 03 ® r-i 1 ^ «“ 1 ^ 1 _ c co co c c co

5 ^ ^ ω ® * S

ή ra -Η - | 22 '2 ra p p ® ® j? 4-> cn j * '+> -r - * ra ra co js: -H ra -t ω ή ® —5 t-ι i—' 03 i — I f-> vm • rt JC 03 03 03 - * ra cl O 'O' 03 "_ £ U03 + JU 4J 03 ® ί! 03 4J JZ JZ £. +3 yy ©

* »+» 000 · -p £ .H

Η -Η -Η Ή Ή '' I t 3 g i-l f-t * -1 = 3 S'-!

IA

CM Q U

C o r »o cj t- * cj

I o I O U O O O

Jj lA CM O ON ^ ® i — t -4J 1 - I vo I * '© ca ia α ι αο ίΤιίί soar ^ a -cf on ^ 0) Q. iH I-H CM NO I — i r-ir-i

PA

CJ

pr \ PA PA CM PA PA

-v- η- 2Π O 3Z3I

CC CJXCJXCJCrtXCJCJX.

rH

<D ___. - ...__: -

-Q ------ tA

X

+> a c ^ s ° ® tn ^ fA cm pa

pa -r -ΤΟ "» * "3 _----: C_) CJ

-η CC U = = - - - - "1-1

O

5 ________ — .--—--—- i *. - o κι

0 »PA. CA

CM X P 't

^ CJ 0Q = CJ - CQCJ - CJX

H '“C -T- OS' XU-ïCJSU .--- ^ 1 * ™ {^ _ 3 CJ - = = = = = = __- __ _____ _ ------ ΓΛ - ws> 5 · - = "-§ - ü X, - = ° = u 1_ ia 'cz • ii O 131

II.3SS3SS535S

800 17 6 δ -20- i. ii

! ι — I ι — 1> H

CO CO CO

x cn c -p -p

c CO -Γ-t (D CO C CO

(U -H -P r — I -H 03 · Η

r — 4 ¢ -4 X (—4 P eP P

r-4 Ü CO - * (“H -M

CO CO 4-) CO

4J (U CO CO CD X CD

me co · ρ c co c —4 X X Ρ · Η · Ρ · Η • 1-5 p 3 CT '-i £ 3 Ρ 3 - · Η Ρ Ρ Ρ

r-t 12 - ® -Ο XI

(4 Ο X C C -Ρ ΟΧ

(U 4-1 X · Η · Η X -Ρ X

χ X ϋ C 3 3 Ο C X Ο C

• Η · Η · Ρ ® Ρ Ρ Ή Ο · Η · Ρ Ο

3 3. - ι ι - ι = = XI X r-ir-43> —ι X

ιτ \ and CM Ο · Η C -ρ

CJCJC-) XCJCJCJCJ

ΙΟΟ 00 οοο ο ο 4J ·· »ro r · * ον ca co <ι · cm cm <r r — ι χ ι ι ι ι <r co ι ο · ι ι <u c cm md co ι co cm ι χ ca

£ 23 ΓΑ <t <r lA 1-4 O CO fA <J

1) α I-1 ι — I r — 4 <r σι ι — I ΓΑ (Hr-)

V

ΓΑ ΙΆ ΓΛ <ι · χ x x ι — 400 CJX O = = X U = = • ί ΐ ~ ~ p

c wee / V T

CO ΙΛ Γ- W —- f / —vl CM

> ΓΑ XX 1 (J X

CM X CM (A 3 3 U

di ce u = = u u m ca ji ι — 4 O _______-_ => - ----------- ------------

P LA

ai x

2S CM CM I-I

cc XU = u = = = = =

1 — I

cc x = = u. = = = = = <—4 Z3 U = = = = = = = = _____.

> <f

CM

--- X

u '-' X 1 = = = = = = = =

I O C X • H

x σι ρ c

<U · Η X CM (A <t ιΛ M3 r- »00 CA

> 3 LA lA ΙΛΙΑΙΑΙΑΙΑ 1Λ1Α ISO 17SÓ -21-!

(“C.

co -p £ Ö Ή u

(D

C

JC -H

• n 3 • H k

r — H _C

tl -P

. x .poe

• rt Ή (U

—I i — I I — it t ~ --- u IA o

CM Q CJ 1A

C O

0 \ lA CJ CJ

| ! I O O

t '... IA IA CM PA

H J ~ "l 1 Q) C P-» <J O · "! Ε 3 <f <0 · PA -Cf 0) Q. ι-H i — I i — I Ή

PA PA PA

<r x x x cc cj x α x o ω x co

-P

c _______----—-- co>

See PA PA

ΐ PA

o CE CJ CJ = s => "'tl

(D

3 »- CM 1—1 cr ll. X = __ <-> - r — i CU X b_ = = __ = _

i-H

3__U = __ = · = __ ï_

> - <i X

^ o = CM ........—

X

CJ

before_H

X I = __- Cj -_ ·· I o c z x cn

PC

¢). - 1 cm, - cm cm

> -Q v £) M3. M3 Ό NO

0601766 -22-

The following examples further illustrate the herbicidal composition of the present invention, although the nature and composition of the components may vary more widely than described.

The parts in the examples are parts by weight.

Composition example 1: Emulsifiable concentrate.

50 parts of the compound No. 3 in 35 parts of xylene and the solution thus formed is mixed with 15 parts of an (8: 2) mixture of polyoxyethylene-10 alkyl phenyl ether and calcium alkyl benzene sulfonate to obtain an emulsifiable concentrate. Before use, the thus obtained composition is diluted with water to form an aqueous emulsion with 0.01 to 1% of the compound No. 3.

15 Composition Example 2: Powder.

5 parts of compound No. 5 are added to 95 parts of clay. 9 and obtained by powder grinding and pulverizing the mixture. It is applied directly to the soil on which the weeds grow or are expected to grow.

Composition Example 3: wettable powder.

A mixture of 50 parts of compound No. 18, 10 parts of diatomaceous earth and 32 parts of kaolin with 8 parts of a (1: 1) mixture of sodium 25-lauryl sulfate and sodium 2,21-dinaphthylmethanesulfonate and obtain a wettable powder by pulverizing the mixture.

Using the composition thus obtained, it is mixed with water to form an aqueous suspension containing 0.06 to 1% of the compound No. 18 contains. Composition Example 4: Granules.

5 parts of a fine powder of compound No. 6 in a solution of 0.5 parts of polyvinyl acetate as a binder in methanol using a suitable mixer to coat 94.5 parts of silica particles (16-32 mesh) to obtain granules. The grains are sprinkled directly in rice fields.

Test Example 1: Pre-treatment under irrigated conditions.

360 1 7 8 § -23-

A certain amount of rice paddy soil I

pots of 1 / 5,000 size were placed in Wagner

to obtain conditions similar to I

in a paddy field and a certain amount of seeds of farm grass, monoehoria, "taothcup", false burnet, I

water plants and rushes sown. I

Furthermore, tubers of arrowhead were 1 cm below the surface of the soil in an amount of 3 pcs

buried per pot and the pot was immersed 3 cm deep. The jar was then diluted

solution of the compound of the present invention

invention in an amount of 0.8 - 50 g of the active compound per are.

After 3 days, three 2.5-stage rice seedlings (variety 15 non-seedable) were transferred from a nursery to each pot. Thirty days after treatment, the herbicidal activity and phytotoxicity were observed

observed with respect to rice. The test results are I.

Valued in the manner stated below and listed in Table 2. I

Herbicide activity index: I.

5: complete weed removal I

4: up to 80¾ weed removal 3: up to 60¾ weed removal 25 2: up to 40¾ weed removal 1 1: up to 20¾ weed removal 0: no effect.

Phytotoxicity index: -: no damage 30 +: slight damage ++: some damage +++: moderate damage ++++: strong damage X: completely dead.

35 3601730

Table 2 Prior treatment under irrigated conditions.

-24- t. __, ____________ compound dose herbicide activity phytotoxidation no. ring farmer-wide [arrowweed rushes g / a grass leaf free-standing ___gen (1) ____ 0.8 5 5 2 1 - 1 3.1 5 5 5 5 12.5 5 5 5 3.1 2 5 4 4 - 2 12.5 4 5 5 5 + 50 5 5 5 5 ++ 0.8 5 5 4.5 5 - 3 3.15 5 5 5 12.5 5 5 5 5 0.8 5 5 3 3 - 5 3 , 1 5 5 '5 5. - 12.5 555 5 -, 0.8 5 5 3 3 6 3.1 5 5 5 5 - 12.5 555 5 - 0.8 5 5 5 5 - 7 3.1 5 5 5 5 - 12.5 5 55 5 standard 3, 1 0 5 0 0 CNP 12.5 4 5 0 0 - not traded 1 I - 0 0 0 0! [___ broadleaf (1): monochoria, "toothcup", v / alse pimpernel, aquatic plants. Standard CNP: compound of formula 23 from the formula sheet.

Table 2 Prior treatment under irrigated conditions.

-25- compound dose- Herbicide activity phytotoxicity thing No. ring - | | j.

g / a farmer's wide arrowwort rushes freestones grass leaves (1) 0.85 5 5 5 13 3.2 5 5 5 5 - 0.85 5 5 5 14 3.2 5 5 5 5 - 0.8 5 5 5 4 - 15 3.2 5 5 5 5 + 0.85 5 3 5 16 3.2 5 5 5 5 + 0.8 5 5 2 5 17 3.2 5 5 5 5 0.8 5 5 1 3 - 19 3.2 5 5 2 5 - 0.85 5 35 21 3.2 5 5 5 5 - 0.85 5 3 4 22 3.2 555 5 _______________ 3.2 5 5! 5 5 23 [12.5 5 5: 5 5 i {

| I

^ f__i____________

Ta fi 5 y 2 2 27 12.5 "4 15 S3 3 1 - 8601753

Table 2 Prior treatment under irrigated conditions.

-26- compound dose- Herbicide activity phytotoxidation No. ring ---- ity g / a farmer's wide arrowwort rushes t. ov rice grass leaves (1) 0.8 5 5 4.5 5 · 29 3.2 5 5 5 5 - 0.85 5 5 5 30 3.2 5 5 5 5 - 0.85 5 4.5 5 34 3.2 5 5 5 5 - 0.85 5 5 5 35 3.2 5 5 5 5 - 0.8 5 5 4 5 37 3.2 5 5 4.5 5 - 0.8 5 5 5 5 39 3.2 5 5 5 5 - 0.85 5 5 5 41 3.2 5 5 5 5 - 0.8 5 5 3 5 46 3.2 5 5 5 5 + standard 12.55 5 0 0 A 25.05 5 3 0 + standard 3.2 5 5 3 0 + B 6 .4 5 5 4.5 0 ++

Standard A (CNP) Standard B

compound of formula 23 (oxadizone): compound of the formula sheet with formula 24 of the formula sheet.

8601766 -27-

As can be seen from the results of Test Example 1 shown in Table 2, each of the tested compounds of the invention showed excellent herbicidal activity against annual and perennial weeds and, in addition, each of the tested compounds was completely safe for the rice seedlings. Test Example 2: Treatment under irrigated conditions after occurrence.

A certain amount of soil from rice fields 10 was placed in Wagner pots with a size of 1 / 5,000 to obtain similar conditions as in a rice field and a certain amount of seeds of farm grass, monochoria, 'toothcup', false burnet, aquatic plants and piping sown.

15 Furthermore, arrowhead tubers in a quantity of 3 pieces per pot were buried 1 cm below the surface of the soil, three rice seedlings in the 2.5-leaf stage (variety: Nihonbare) were transferred from a nursery, the pots were 3 cm flooded and then placed in a greenhouse.

When the weeds reached the 1 to 2 leaf stage, a dilute solution of the wettable powder of the compound of the present invention in an amount of 3.2 to 12.5 g of the active compound per acre was added to the irrigation added.

After 30 days of treatment with the dilute solution, the herbicidal activity was observed to yield the results listed in Table 3. The basis for the valuation of the results is the same as in Test Example 1.

800 1 7 6 6

Table 3 Treatment under irrigated conditions after occurrence -28- compound dose- Herbicide activity phytotoxicity --- no. ring g / a farmer's wide arrowwort piping compared to

grass leaves (1) 3.2 5 5 5 5 - 14 __12,3 3__5__5__5 __ + _ 3.2 5 5 4 3 15 __12,5 5__5 4,5__4,5 _ 3.2 5 5 4,5 5 17 __12,5 5__5__5__5 __ + _ 3.2 4 5 1 5 18 __12.5 5__5__4__5 __ ++ _ 3.2 4 5 2 3 - 19 __12.5 5__5__4__5 __ + _ 3.2 5 5 3 3 - 20 __12.5 5__5__4__5 __-_ 3.2 5 5 4 5 - 21 __12.5 5__5__4__5 __ + _ 3.25 5 3 3 29 __12.5 5__5__4__4 __ + _ 3.2 5 55 5 30 '_12.5 5__5__5__5 __ + _ 3.25 5 5 5 31 12.5 5 5 5 5 + _i____J__ 860 1 7 6δ

Table 3 Treatment under irrigated conditions after occurrence -29- compound dose- Herbicide activity phytotoxidation No. ring - 1 ---— quality g / a farmer's broad-arrowhead edging relative to

grass leaf rice ___gen (1) ___ 3.2 5 5 4 5 39 __12.5 5__5__5__5 __-_ 3.2 5 5 4.5 5 41 __12.5 5__5__5 _; __ 5 __-_ 3.2 5 5 3 4 - 46 __12.5 5__5__5__5 __-_ 12.5 3 5 0 0

standard A.

_1 25.0 5_5_ [o_ | _0 _ [+ __

Standard A: the same as in Test Example 1

86017SS

r -V

-30-

As can be seen from the results of Test Examples 1 and 2 shown in Tables 2 and 3, each of the tested compounds of the invention showed excellent herbicidal activity against 1-5 and perennial weeds in rice paddies in common post-treatment treatments and treatments. and furthermore, each of the tested compounds of the invention was completely safe for the rice seedlings when applied to the soil before and after planting.

10 The following test examples relate to farming.

Test Example 3;

A certain amount of soil was placed in a round plastic vessel with a diameter of 8 cm and a height of 8 cm and a certain amount of seeds of blood millet, foxtail, parrot herb and chenopodium album was sown, after which the seeds were covered with a layer of soil from 0.5 to 1 cm. Then, a dilute solution of the compound of the present invention was immediately applied to treat the entire surface of the soil in an amount of 3.2 to 50 g of the active compound of the invention per acre.

After the treatment, the cultivation was carried out in a greenhouse and the herbicidal activity was observed on the 20th day. The test was run with 2 repetitions and each mean value was determined. The standard for evaluating the results is the same as in Test Example 1. The test results are shown in Tables 4 and 41.

30 8601788 -31-

Table 4 Preliminary surface treatment of the soil.

compound dosage herbicide activity g / a —----— chestnut millet parrot- Chenopodi-tail herb urn album 12.5 2 2 4 4.5 50 3 3 5 5 12.5 5 5 5 2 50 55 5 5 12.5 555 5 3 50 555 5 12.5 5 5 5 5 5 50 5 5 5 5 12.5 5 5 5 5 6 50 5 5 5 5 12.5 5 5 5 5 7 50 5 5 5 5 standard 12.5 2 3 5 5 nitrophen 50 5 5 5 5 not treated - 0 0 0 0

Standard nitrophen: the compound of formula 25 of the formula sheet.

8üÖ17 -32-

Table 4 'Prevent surface treatment of the soil.

compound dosage Herbicidal activity fox-millet-parrot Chenopodi -__ tail___weed__urn album 3.2 3 4 5 5 14 12.5 55 5 5 3.2 2 3 5 5 15 12.5 45 5 5 3.2 3.5 3 5 5 17 _ 12.5 5__5__5__5_ 3.2 1 1 5 5 19 __12.5 2__3__5__5_ 3.2 2 1 5 5 21 __12.5 4__YYY__5__5_ 3.2 2 3 5 5 - 22 12.5 4.5 4__5__5_ 3.2 4 4 5 5 29 _ 12.5 4.5 5__5__5_ 3.2 3 3 5 5 32 _12,5 '4' __ 4__5__5_ 3.2 4 4 5 5 35 _ 12.5 4.5 5 __5__5_ 3.2 4 4 5 5 39 _12.5__5__5__5__5_ 3.2 2 2 5 5 46 _12,5__3__3__5__5_ 3.2 12 3 2

standard C.

_12.5 4 1 5_ 5 _ [_ 5_

Standard C (Simazine): compound of formula 26 of the formula sheet.

8601766 -33-

Trial example 4:

A certain amount of soil was placed in a plastic vessel measuring 23 cm x 45 cm x 12.5 cm and a certain amount of seeds of soybeans, cotton, 5 corn, wheat, sunflowers and rice was sown, after which the seeds were covered with an approximately 3 cm thick layer of soil.

Then, a dilute solution of the compound of the present invention was immediately sprayed onto the soil surface using a small sprayer in an amount of 12.5 to 50 g of the active compound of the present invention per are.

After the treatment, the productive crops were grown in a greenhouse and 20 days later, the degree of phytotoxicity with respect to each of the productive crops was observed. The test was run with 2 repetitions and each mean value was determined.

The standard for evaluating the test 20 results is the same as in Example 1 and the results are shown in Table 5.

800 170-3 -34-

Table 3 Test example 4 compound dosage Phytotoxicity compared to productive thing g / a _3 ___

No. soybeans cotton corn wheat rice sunflowers 12.5 - - 50 - + + 12.5 - - - 2 50 π + ++ ++ ++ - 12.5 - - - - 3 50 - - - 12.5 - _____ 5 50 - _____ 12.5 - - _ 6 50 - _____ 12.5 - - - 7 50 - _____ 8 5 A .3 «**. .

öv i / U

-35-

Table 5 Test Example 4 Compound Dosage Phytotoxicity vs. Productive No. g / a washed soybeans cotton corn 12.5 - - - 14 _ 50 __ = __ ++ ___ 12.5 - 15 _______ 50 __ = __ ++ __ I_ 12.5 -17 __50 __ = __ j: __ = _ 12.5 - - 19 __50 __ = _; __ = ___: _ 12.5 21 __50 __-____- 12.5 - - 22 _______ 50 __ = __-__ = _ 12.5 - '- 29 __50 __ = __ = ___ 12.5 32 __50 ___-__: __-___ 12.5 - - 35 __50 _____-_ -_ 12.5 - ~ - 39 __50 __ = __-__ 12.5 - - 46 __50 _-__-_-______ 12.5 ++ ++

standard C.

__50_j ++ - t -__ +++ _ -F + _

Standard C: the same as in test example 3 860 1 7 ·; ·; -36-

Test example 3: Treatment after the occurrence.

In a farm soil in a plastic pot with a diameter of 8 cm and a depth of 8 cm, a certain amount of seeds of the 5 weeds mentioned in table 7 were sown and the weeds were grown in the pots. When the weeds were in the third to fourth leaf stages, a liquid prepared by diluting a wettable powder formed using the compounds of Table 7 to obtain 3.2 to 50 g of the present compound per 100 m from the surface of the soil in the pot, sprayed on the weeds in the pot. The test was performed with 2 repetitions. After 20 days, the herbicidal activity on the weeds was tested, the extent of the herbicidal activity being evaluated according to the same criteria as in the Example 1 and shown in Table 6.

-37-

Table 6 Post-Treatment Treatment ί Compound Dose Herbicide Compound Dose Herbicide No. ring activity thing No. ring activity g / a fox- pape- g / a fox- pape- tail jay- tail jay- ____ spice '____; __ spice 12.5 2 5 "3.2 2 4 * __ 50 3__5 __ ^ __ 12.5 3__4.5 12.5 2 5 3.245 2 29 __50 15__5 ___ 12.5 5_J_ 12.5 3 5 3.2 4 5 3 30 '__50 4__5__12.5 5__5_ 12.5 4 5 “3.2 4 5 5 34 __50 5 5 ___ 12.5 5__5 HTB [5 5” 5.2 4 5 10 36 50 5 5 12.5 5 5 12.5 2 5 "3.2 5 5 11 37 __50 5__5 ____ 12.5 5__5__ not treated 3.24 5 traded 0 0 40 12 5 5 5 - - 5: JT2 4 5 13 42 12.5 4.5 5 12.5 5 5 3.2 4 5 "3.2 3 5 14 46 ___ 12.5 4.5 5 ___ 12.5 4 5_ 3.2 1 5" 3.2 5 5 15 48 12.5 4__5 ______ 12.5 5__5_ 3.2 4 5 standard 3.2 3 '5 - ^ 2 5 5 5 standard D 12.5 5 5 yy - - = 17 12.5 5 5 3.2 4 5: 19 12.5 4.5 5 3.2 1 Γ1 “- 21 __12.5 5 15 11___

Standard D: compound of formula 27 from the formula sheet.

6601765

T

-38-

As can be seen from the results of Test Examples 3 to 5, the present compounds exhibit excellent herbicidal activity against the major weeds in harvesting fields in occurring treatments and post-treatment treatments, and as shown by the results of the Test Example 4, the present compounds do not harm the productive crops, so that the compounds can accordingly be suitably used as herbicides on ordinary agricultural soils.

-conclusions-

Claims (3)

A compound of formula 1 of the formula sheet, wherein a hydrogen atom, halogen atom or methyl group, 5. a hydrogen atom, halogen atom or lower alkyl group, RJ an optionally substituted lower alkyl group by a halogen atom or the methylsulfonyl group, an optionally by a halogen atom or the nitro group substituted 4 benzyl or phenyl group, R a hydrogen atom, a lower alkyl group optionally substituted by a carboxyl or lower alkoxycarbonyl group, a lower alkenyl group, lower alkynyl group, methylsulfonyl group or optionally halogen substituted benzyl group, X a hydrogen atom, halo or C ^ -C 2 -alkyl group and Y represents a C 1 -C 2 -C 15 alkyl group, or X together with Y forms the group - (CH 2) -j- or, and W represents a halogen atom. * 2. Compounds according to claim 1, wherein R 2 is a fluorine or chlorine atom, R a chlorine or methyl group, R a lower alkyl group, R a methyl, ethyl, 20. carboxymethyl or methoxycarbonylmethyl group, X a chlorine atom and Y represents a methyl group or X together with Y forms the group - (Cf ^) ^ -, and W represents a chlorine atom. Compounds according to claim 1, wherein R 1 * 2 is a fluorine or chlorine atom or methyl group, R a chlorine 3 4 25 or bromine atom or methyl group, R -SC ^ CF ^, R a hydrogen atom, X a hydrogen, chlorine or bromine atom or methyl group and Y represents a methyl group or X together with Y forms the group - (Cf ^) ^ -. 4. Compounds according to claim 2, in which R 1 represents a fluorine atom, R represents a chlorine atom, R represents a methyl or ethyl 4 group, R represents a methyl, carboxymethyl or methoxycarbonylmethyl group, X represents a chlorine atom and Y represents a methyl group, or X together with Y forms the group, and W represents a chlorine atom. Compounds according to claim 1 selected from the group of compounds of formulas 16 to 22 of the formula sheet. 6. Process for the preparation of compounds 12 of the formula I of the formula sheet, wherein R, R, R, 40 W, X and Y have the meanings mentioned in claim 1 8O177S TC-40- and is a hydrogen atom, having characterized in that a compound of the formula III of the formula-I2 sheet wherein R, R, W, X and V have the meanings mentioned in claim 1 is reacted with a compound 5 of the formula 4 'or a compound with the formula 4 of the formula sheet. 7. Process for the preparation of a compound 12 3 of the formula 1 of the formula sheet, wherein R, R, R, W, X and Y have the meanings mentioned in claim 1 and R and optionally a carboxyl or lower alkoxycarbonyl group substituted lower alkyl group, a lower alkenyl group, a lower alkynyl group, the methylsulfonyl group or any benzyl group optionally substituted by a halogen atom, characterized in that a compound of the formula 5 of the formula is presented, wherein R, R, R, X, Y and W have the aforementioned meanings, react with a compound of the formula 6 of the formula sheet or a compound 4 of the formula 6 'of the formula sheet, wherein R is optionally given by a carboxyl or lower alkoxycarbonyl group substituted lower alkyl group, a lower alkenyl group, a lower alkynyl group, the methylsulfonyl group or an optionally halogen substituted benzyl group and Hal a halogen atom for organizes. 8. Process for the preparation of a compound 12 3 of the formula 1 of the formula sheet, wherein R, R, R, 4 R, X, Y and W have the aforementioned meanings, characterized in that a compound having 2 formula 1 of the formula sheet, wherein R is a hydrogen atom and R, R, R, X, Y and W have the meanings mentioned above, reacts with a halogenating agent. A herbicide composition, characterized in that it has an effective amount of a compound of the formula 1 of the formula sheet, 12 3 4 wherein R, R, R, R, X, Y and W have the meanings set out in claim 1 , and contains one or more additives. A composition according to claim 9, characterized in that R 1, R 2, R "5, r x, Y and W have the meanings set out in claim 2. 11. A composition according to claim 9, characterized in that R ^, R ^, R ^, R ^, X, Y and W have the meanings mentioned in claim 3. The composition according to claim 10, characterized in that R ^, R ^, R ^ X, Y and W have the meanings mentioned in claim 4. The composition according to claim 9, characterized in that the active ingredient 10 is selected from the group of compounds of formulas 16 to 22 of the 14. Weed control method, characterized in that an effective amount of a compound of the formula 1 of the 12 3 4 15 formula sheet, wherein R, R, R, R, X, Y and W have the meanings mentioned in claim 1. applied to the weed or its location 15. Method according to claim 14, characterized in that r \ R ^, R ^, r \ X, Y and W are the ones claimed in claim 2. g have the same meanings. A method according to claim 14, characterized in that R, R, R, R, X and Y have the meanings mentioned in claim 3. A method according to claim 14, characterized in that R 1, R 1, R 1, R 1, R 1, X, Y and W have the meanings mentioned in claim 4, A method according to claim 14, characterized in that the active ingredient is selected from the group of the compounds of formulas 16 to 22 of the formula sheet. 860 1 7 e δ y VV 't' · .so ~ r3 ^ —R2 ^ Ί '^ »Γ W N0o' W NH- / 2 y 2 Y'r ^ v \ / ^ y * ^^ / γ ^: \ RR (2) (3) WW NHSO-R3 NH_., XA \ / 2 ^ (R “SC ^) 2 ^ (4) I ft γ 2 V / VR -r - ^ - Γ 3k7 VR ^ Αν ^ γ1 \ / o £ R -S02 “H9! (4) y> · ^ Asr \ - / E (5) (3) ï / ^ 0 ^ 3 1 7v2R3 '' yNu / V2 (r4 °> 2s ° 2.hl.sy> |) -s2 Y ^ * % / \ = / or R4-Hal (6) · \ = / k a1 (5) (1) W 3 W _J <S ° 2R N'502R T> 0 * '. . Yvfpl. / \ = / Halogenating agent / \ - / r1 * y b1 (7) '(1) w 0 no2 1 ^ ° 2 // \ v__R2 ^ y \ ft 2 Halogenating agent T \ / Ύ / -w "R--: —ΆΧ / rA tn 4 HR '* (2) (8) WWL 1 n 7 χαΑΧιχγΥΧ Fr - [/ y = J {Y r1 R (2) (9) 0. R6 9 ^ 6 x - OR5 h2n.hn - / ^ - r> Y> rj4l · - / \ -R2 X + / X7 AYRH (ii) (12) (10) UJJ R6. H2N-ζ ~ \ -R2 R1 (13) W 7 V rj XA - XX "YN j / l R1 950 17 es 1141 <15 '-4Γ ...... * ^ CH3 Cl r / - ^ Nsso2ch3 / -fiS02f: F3 ^ / - (0 / - ° 1 \ 0 / C1' - PH / 0é) i'V 01 XsfcH ^ 51 ^ S ° 2C2H5 2CH3 / f CH-C00H ^^ / N_ ^ 0) -C1 [J ^ J> Vo) _cl2 f * 8) f'9) Cl N ^ CH C = CH - / S02CH3 / Α, Α y ^ nS02CH3 _P ^ CH2C00H χχ x ~ / o) -ci .ch9cooh ^ Cv'TV1 “F Cl / ^) - 0-ΚΊ — NO- c«) VI V) Cl f3 f-Ni — Ó ~ C1 AC1 CH _C-10J_o M .ch5 Qf> -0 _ / \ I öch <ch3 \ = A-no2 Ü,) C ") Cl" Η -Ψ N / COONa '2¾ N Y— N-C h CFr ^^ C-_ n / T ~ /, tl' 2 5 3 W ^ 0-TV.no2 86017 36 '(tf)