CS227044B2 - Herbicide - Google Patents

Description

The present invention relates to a herbicidal composition comprising as an active ingredient at least one N- (2-fluoro-4-halo-5-substituted phenyl) -3,4,5,6-tetrahydrophthalide derivative (hereinafter referred to as "tetrahydrophthalimide") ) as well as the method of manufacture of the active substance.

These tetrahydrophthalimides can be represented by formula (I)

where

X represents a chlorine atom or a bromine atom and

R represents an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or sec-butyl; (C 3 -C 4) atoms, for example allyl, or (C 3 -C 4) alkynyl, such as 2-propynyl.

Certain N-phenyltetrahydrophthalimide derivatives are known to be potent herbicides. For example, the herbicidal use of 2-fluoro-4-chlorophenyltetrahydrophthalimide, 2,4-dichloro-5-isopropoxyphenylltetrahydrophthalimide, etc. is described in U.S. Pat. No. 4,032,326 or British Patent No. 2,046,754 A. However, the herbicidal activity of these of substances is still not satisfactory in all cases.

It has now been found that the tetnahydrophthalimides of formula (I) exhibit significant herbicidal activity against a wide variety of weeds including grass weeds, broadleaf weeds and broadleaf weeds at low doses and have no significant phytotoxicity to various agricultural crops. Examples of weeds from the grass family against which the tetrahydrophthalimides of the formula I are herbicidally active are Echinochloa crus-galli, Setaria viridis, Digitaria sanguinalis, Sorghum halepensej, Deaf oat ( Avena flatua), Alopecurus geniculatus, Eleusine indica, Poa annua, Cynodon dactylon, Agropyron repens etc.

Examples of sediments are the sediments sp. (Cy.perus sp.J, Flatsedge (Cyperus rotundus), Flatsedge (Cyperus serotinus), Scirpus juncoides, Eleocharis kuroguwai, Eleocharis acicularis, etc.

Examples of broadleaf weeds are Ipomoea purpurea, Abutilon theoprasti, Cassia obtusifolia, Sunflower (Helianthus annus), Xanthium pennsylvanicum, Brassica kaber, Stellaria media , Cucumber Durman (Datura stramonium), Sesbania exaltata, Euphorbia helioscopiaj, Sida spinosa, Ambrosia (Ambrosia artemisifoliia), Cottonwood (Polygonům sp.j, Amaranthus retroflexus), (Matricaria sp.j, Persian Speedwell (Veronice persioaj, Buckwheat Buckwheat (Polygonum coruvolvulus)), Cottonweed (Polygonum persicaria Bidens sp.), Saucepan (Chenopodium album), Black Eggplant (Solar nigrum), Braid (Salystegia japonica) Monochoria vaginalis, stamina (E latine americana j, Linderia procumbens, Rotala indica, arrowhead (Sagittaria pygmaea).

Accordingly, they are suitable for use as herbicides in crops and vegetables as well as rice. They can also be used as herbicides for the treatment of orchards, lawns, pastures, gazebos, mulberry groves, rubber plantations, forests, etc.

Tetrahydrophthalimide of formula (I) according to the invention is prepared by the preparation of hydroxyphenyltetrahydrophthalimide of formula (III)

where

X is as defined above, reacted with a halide of formula

R - Y, where

R is as defined above, generally in an inert solvent such as dimethylformamide or dimethylsulfoxide in the presence of a base such as an alkali metal carbonate such as potassium carbonate, an alkali metal hydroxide such as potassium hydroxide, an alkali metal hydride such as sodium hydride or an alkali alkoxide a metal such as sodium methoxide or sodium ethoxide. The most preferred base is an alkali metal carbonate. The reaction temperature is. usually in the range of 0 to 100 ° C, preferably in the range of 40 to 90 ° C. The ratio of the molar amount of hydroxyphenyl-tetrahydrophthalimide of formula III to the molar amount of halide of formula RY is preferably in the range of 1: 1.0 to 1: 1.1.

The tetrahydrophthalimide (I) thus obtained may optionally be purified by a known method, for example by recrystallization or column chromatography.

The hydroxyphenyltethahydrophthalmide of formula (III), which is the starting material of the process of the invention, can be prepared from a phenol of formula (IV).

where

X is as defined above, according to the scheme below:

HIM

Y represents a chlorine atom, a bromine atom or an iodine atom and (V)

S kde

X is as defined above.

Thus, the hydroxyphenyltetrahydrophthalimide III can be prepared from the phenol IV by nitration, whereupon the resulting nitrophenol V is reduced and the aminophenol VII obtained is treated with an acid anhydride

3,4,5,6-tetahydrophthalic.

The conversion of the phenol of the formula IV into the nitrophenol of the formula V can be carried out by a known process for nitration of the phenol of the formula IV. Typically, however, indirect nitration is preferred, consisting of the following three steps to achieve selective nitration at the desired position:

where

X is as defined above.

In the first step, the phenol of formula (IV) is converted to its alkali metal salt by treatment with an aqueous alkali metal hydroxide solution, such as sodium hydroxide or potassium hydroxide, and reacting the resulting salt with an alkyl halide such as methyl ester chloroform, in water at a temperature between 0 and 10 ° C. The ester (VIII) thus prepared is nitrated with a mixture of concentrated sulfuric acid and concentrated nitric acid at room temperature. Then, the resulting nitrobenzene (IV) is hydrolyzed with an aqueous alkaline solution, such as aqueous sodium hydroxide, at a temperature in the range of 20 to 120 ° C to give the nitrophenol (V).

Conversion of the nitrophenol of formula V to the aminophenol of formula VII can be accomplished by any known reduction process for converting a nitro group to an amino group. Examples of such reduction processes are catalytic reduction, iron powder reduction, sodium sulfide reduction, sulphated sodium borohydride, etc. reacting 1 mole of nitrophenol V with 3 moles of hydrogen in the presence of 0.1 to 0.01 mole of platinum oxide in an inert solvent such as ethanol or ethyl acetate at room temperature at atmospheric pressure to give the aminophenol VII. Also, for example, by reacting 1 mole of nitrophenol of formula V with 2 to 5 moles of iron powder such as reducing iron or electrolytic iron, in a 5% acetic acid solution or in a dilute hydrochloric acid solution, at a temperature in the range 80-100 ° C for After 1 to 5 hours, the aminophenol VII is obtained.

For the preparation of the hydroxyphenyl-tetrahydrophthalimide III from the aminophenol VII, this aminophenol is reacted with an acid anhydride

3,4,5,6-tetrahydrofthalic acid in an inert solvent such as acetic acid at reflux for 1 to 6 hours, preferably 2 to 4 hours.

However, the phenol of formula IV has been described by Finger et al. in J. Am. Chem. Soc., 81, 94 (1959).

A presently preferred and practical embodiment of the preparation of the tetrahydrophthalimide of formula (I) as well as of intermediates including the intermediate of formula (I)

RO where

X is as defined above, as described in the examples below.

Example 1

Preparation of tetrahydrophthalimide of formula I

To a solution of 1 g of N- (4-chloro-2-fluoro-5-hydroxy-phenyl) -3,4,5,6-tetrahydro-phthalimide in 10 ml of dimethylformamide was added 0.34 g of anhydrous potassium carbonate with stirring at room temperature. The reaction mixture is then stirred for 30 minutes at about 40 ° C, 1 g of propargyl bromide is added thereto, and the mixture is stirred at 50 to 60 ° C for 3 hours. The mixture is then allowed to cool to room temperature. Pour into water and extract with ether. The ether layer was washed with water, dried over anhydrous sodium sulfate and concentrated. The concentrated residue was purified by silica gel chromatography to give 0.8 g of N- [4-chloro-2-fluoro-5- (2-propynyloxy) phenyl] -3,4,5,6-tetrahydrophthalimide (Compound No. 10). melting point

136.4 ° C.

Elemental analysis calculated:

% C, 61.09;% H, 4.00;% N, 4.20; found:

% C, 61.18;% H, 4.19;% N, 3.92.

NMR (CDC1 ₃₎ (ppm.)

1.8 (4H, m);

2.4 (4H, m)

2.55 (IH)

4.7 (IH)

6.95 (1H, d, J = 6Hz),

7.25 (1H, d, J = 10Hz).

IR spectrum at ^nuo [cm ^-1 ]: 3260, 1700.

Example 2

Preparation of tetrahydrophthalimide of formula I

To a solution of 2.95 g of N- (4-chloro-2-fluoro-5-hydroxyphenyl) -3,4,5,6-tetrahydrophthalimide in 20 ml of dimethylformamide was added 7.6 g of anhydrous potassium carbonate and 1.6 g of n. -amyl bromide, respectively. The resulting mixture was stirred at 70-80 ° C for 3 hours. Water was then added and the mixture was extracted with ether. The ether layer was washed with water, dried and evaporated. The evaporation residue is purified on silica gel chromatograificky, yielding 0.63 g of N- (4-chloro-2-fluoroanilino ^and R-5-n-amyloxyf enyl) -3,4,5,6-tetrahydrophthalimide (Compound no. 13) mp 100.8 ° C.

NMR spectrum? (Ppm):

0.9 (3H, t, such as m),

1.5 (4H, m)

1.8 (6H, m)

2.4 (4H, m);

3.9 (2H, t, I = 6Hz)

6.65 (1H, d, J = 6Hz),

7.25 (1H, d, J = 10Hz).

Examples of the tetrahydrophthalimide of formula (I) prepared by the process of the invention are shown in Table I.

Table I

Compound No. X

R Physical properties

1 WHOSE iso-C ₃ H ₇ - mp 81-82 ° C 2 Br iso-C ₃ H ₇ - mp 116.5-117.5 ° i 3 Cl CH, - mp 115.2 ° C 4 Cl c ₂ h ₅ - m.p. 90-91 ° C 5 Cl , nC ₃ H ₇ - o _D ²² 1.5472 6 Cl sec.-C / jHg— n _n ²³ · ⁵ 1.5512 7 Cl 1SO-C4H9— mp 58-59 ° C 8 Cl ch ₂ = chch ₂ mp 56-57 ° C 9 Cl ch ₂ = chch - 1 ch ₃ n _D ^25.5 1.5512 10 Cl ch = cch ₂ mp 136.4 ° C 11 Cl n-CiHg— m.p. 74-75 ° C 12 Cl CH ₃ CH = CCH- mp 115-116 ° C 13 Cl nC _with H _u - mp 100.8 ° C 14 Cl ⁿ * C6H ₁₃ - m.p. 60-61.6 ° C 15 Dec Cl nC _{7 H15} - n _D ²⁵ · ⁵ 1.5381 16 Cl nC ₈ H _{] 7} - n _D ²⁵ - ⁵ 1.5303 17 Cl iso-CjHu - mp 85-87 ° C 18 Br CH, - mp 105-106 ° C 19 Dec Br C2H5- mp 110-111 ° C 20 May Br nC ₃ H ₇ - mp 76-77 ° C 21 Br sec.-C, ₄ H ₇ - mp 84.5-85.5 ° C 22nd Br CH-CCH mp 127-128 ° C 23 Br ch ₂ = chch ₂ mp 69-70 ° C

Example 3

IR spectrum ν (cm ^-1 ): 3380, 1680.

Preparation of a hydroxyphenyl-tetrahydrophthalimide of formula III wherein X is Cl

6.6 g of 2-chloro-4-fluoro-5-aminophenol and 6 g of 3,4,5,6-tetrahydrophthalic anhydride are dissolved in 20 ml of acetic acid, and the solution is refluxed for 2 hours. The reaction mixture was allowed to cool to room temperature, then poured into ice water and extracted with ether. The ether extract was washed with saturated sodium bicarbonate solution and water, respectively, then dried over anhydrous magnesium sulfate and concentrated. The residue is chromatographed on silica gel to give 4.0 g of N- (4-chloro-2-fluoro-5-hydroxyphenyl) -3,4,5,6-tetrahydrophthalimide, m.p. 151 ° C.

NMR Spectrum (CDCl ₃ , D ₆ -DMSO 3 δ (ppmj:

1.5-2.0 (4H, mj,

2.1-2.6 (4 H, m),

6.8 (1 H, d, J = 6 Hz),

7.15 (1H, d, J = 10Hz).

Example 1 a d 4

Preparation of the hydroxyphenyl-tetrahydrophthalimide of formula III wherein X is Br

Using the procedure of Example 3, but using 2-bromo-4-fluoro-5-aminophenol instead of 2-chloro-4-fluoro-5-aminophenol, N- (4-bromo-2-fluoro-5-hydroxyphenyl) was prepared. 3,4,5,6, tetrahydrophthalimide, m.p. 167-168 ° C.

Nuclear Magnetic Resonance Spectrum (CDCl ₃ , D 6 -DMSO) δ (ppmj:

1.5-2.0 (4H, mj,

2.1-2.7 (4H, mj,

6.8 (1H, d, J = 6Hz),

7.25 (1H, d, J = 10 Hz).

IR spectrum vj ^{5 "1} (cm ^-1): 3380, 1690th

12

Example 5

Preparation of an aminaphenol of formula VII wherein X is Cl

A suspension of 9.17 g of 2-chloro-4-fluoro-5-nitrophenol and 500 mg of platinum oxide in 120 ml of ethanol is subjected to catalytic reduction with hydrogen at room temperature and atmospheric pressure until the specified amount of hydrogen has been taken up. Then the catalyst is filtered off and the filtrate is concentrated. The residue is concentrated with ether. The ether layer was concentrated to give 6.6 g

3-amino-6-chloro-4-fluorophenol, m.p. 143-146 ° C (dec.).

Nuclear Magnetic Resonance Spectrum (CDCl ₃ , D _G- DMSO) δ (ppm):

6.4 (1H, d, J = 8Hz);

6.85 (1H, d, J = 11Hz).

IR spectrum v (cm &^lt; -1 & gt ^; ): 3400.3320.

Example 6

Preparation of an aminaphenol of formula VII wherein X is Br

Following the procedure of Example 5, but substituting 2-bromo-4-fluoro-5-nitrophenol in place of 2-chloro-4-fluoro-5-nitrafenol gave 3-amino-6-bromo-4-fluorophenol, m.p. 129 - 130.5 ° C (dec.).

NMR Spectrum (CDCl 3, D ₆ -DMSO) δ (ppm):

6.57 (1 H, d, J = 8 Hz),

7.1 (1H, d, J = 11Hz).

IR spectrum 3400.3320.

Example 1 a d 7

Preparation of a nitrophenol of formula V wherein X is Cl

To a solution of 27.7 g of sodium hydroxide in 450 ml of water is added 83.4 g of 2-chloro-4-fluorophenol and dropwise at a temperature below 10 ° C.

69.2 g of methyl chloroformate. The precipitated crystals were filtered off and washed with water to give 134.8 g of (2-chloro-4-fluorophenyl) formic acid methyl ester, m.p. 69-71 ° C.

The obtained 134.8 g of (2-chloro-4-fluorophenyl) formate, prepared as described in the preceding paragraph, is suspended in 50 ml of concentrated sulfuric acid. To this suspension at a temperature of about 30 ° C is added a mixture of 50 ml of concentrated sulfuric acid with 50 ml of concentrated nitric acid, and the mixture is stirred at that temperature for 1 hour. The reaction mixture was poured into ice water, the precipitated crystals were filtered off and washed with water. 143 g of (2-chloro-4-fluoro-5-nitrophenyl) formic acid methyl ester of melting point 53-55 ° C are obtained.

The product obtained above was added to a solution of 27 g of sodium hydroxide in 300 ml of water and the resulting mixture was heated under reflux for 4 hours. Using celite (filter aid), the precipitated insoluble matter is filtered off and the filtrate is acidified with concentrated hydrochloric acid. The precipitated crystals were collected by filtration and washed with water to give 76.3 g of 2-chloro-4-fluoro-5-nitrophenol, m.p. 106-107 ° C.

NMR (CDC1 _3, D ₆ -DMSO) s (ppm):

7.25 (1 H, d, J = 10 Hz),

7.64 (1 H, d, J = 6 Hz).

IR spectrum ^S1 (cm ^<4): 3370th

Example 8

Preparation of a nitrophenol of formula V wherein X is Br

To a solution of 7 g of sodium hydroxide in 100 ml of water was added 28 g of 2-bromo-4-fluorophenol, and methyl chloroformate was added dropwise at a temperature below 10 ° C. The precipitated crystals were filtered off and washed with water (yielding 41 g of (2-bromo-4-fluorophenyl) formic acid methyl ester, m.p. 80.7 ° C).

The (2-bromo-4-fluorophenyl) formic acid methyl ester thus obtained is suspended in 13 ml of concentrated sulfuric acid. A mixture of 13 ml of concentrated sulfuric acid with 13 ml of concentrated nitric acid is added to the resulting suspension at a temperature of about 30 degrees Celsius. The resulting mixture was stirred for 30 minutes and then poured onto crushed ice. The precipitated crystals were washed thoroughly with water to wash. There are obtained 38.3 g of yellow crystals of (2-bromo-4-fluoro-5-nitrophenyl formic acid) methyl ester of melting point 63.5 to 64.5 ° C.

The product thus obtained was refluxed for 3 hours together with 6.2 g of sodium hydroxide and 100 ml of water. Insoluble matter was filtered off and the filtrate acidified with hydrochloric acid. The precipitated crystals were filtered and washed with water to give 25 g of 2-bromo-4-fluoro-5-nitrophenol, m.p. 126-127 ° C.

NMR Spectrum (CDCl ₃ , D ₆ -DMSO) δ (ppm):

7.42 (1 H, d, J = 10 Hz),

7.65 (1 H, d, J = 6 Hz).

IR spectrum ^ ° ¹ (cm ^"1): 3450th

When the tetrahydrophthalimides of the formula I are used in practice, the compounds can be applied as such or in any form of administration such as wettable powders, emulsifiable concentrates, granules, suspensions or dusts.

In the manufacture of these dosage forms can be solid or liquid ^nose: Ce. Suitable solid carriers are mineral powder substances (e.g. kaolin, bentonite, montmorillonite, talc, diatomaceous earth, mica, veirmikulite, gypsum, ammonium carbonate, apatite, synthetic silica containing water), ground vegetable substances (e.g. soybean meal, wheat flour, wood flour, tobacco flour, starch, crystalline cellulose], high molecular weight compounds (e.g., petroleum resins, polyvinyl chloride, damar resin, ketone resin), alumina, glycerol, and the like.

With regard to liquid carriers, for example, alcohols (e.g. methanol, ethanol, ethylene glycol, benzyl alcohol), aromatic hydrocarbons (e.g. toluene, benzene, xylene, methylnaphthalene), halogenated hydrocarbons (e.g. chloroform, carbon tetrachloride, monochlorobenzene), ethers ( e.g. chloroform, carbon tetrachloride, monochlorobenzene], ethers (e.g. dioxane, tetriahydrofuran), ketones (e.g. acetone, methylethylketone, cylohexanone), esters (e.g. ethyl acetate, butyl acetate, ethylene glycol acetate), acid amides (e.g. dimethyiformamide), acid nitriles (e.g. acetonitrile) , ether alcohols (e.g. ethylene glycol ethyl ether), water and the like.

The surfactants used for emulsifying, dispersing or dispersing can be any of the nonionic, anionic, cationic and amphoteric types of these agents. Examples of surfactants include polyoxyethylene alkyl ethers, polyoxyethylonalkylarylethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, oxyethylene polymers with oxypropylene, polyoxyethylene alkyl phosphates, fatty acid salts, alkyl sulfates, alkyl sulfates, alkyl sulfates, alkyl sulfates, alkyl sulfates. However, surfactants (agents used in the composition of the invention are not, of course, limited to these compounds. If necessary, gelatin, casein, sodium alginate, starch, agar, polyvinyl alcohol, ligninsulfonic acid and the like can also be used as auxiliary agents. ,.

In the preparation of the herbicidal composition according to the invention, the tetrahydrophthalimide I can be used in an amount of from 1 to 95% by weight, preferably from 3 to 80% by weight.

The tetrahydrophthalimide of formula (I) contained in the composition of the invention as an active ingredient can be used together with other herbicides to improve the herbicidal activity of the herbicides, and in some cases synergistic effects are expected. Furthermore, the tetrahydrophthalimides of the formula I can be used in combination with insecticides, non-methocides, fungicides, plant growth regulators or fertilizers, as required in individual cases.

The application rate of tetrahydrophthalimide (I) may vary depending on which tetrahydrophthalimide is used, the type of crop to be grown, the method of application, etc. However, an application rate of from 0.01 to 5 kg, preferably from 0, is generally employed. , 05 to 3 kg of active ingredient per ha.

The examples below describe formulations of the herbicidal composition of the invention suitable for practicing use. Parts and percentages are by weight.

Formulation examples

Example 1 parts of Compound No. 1, 2 or 3, 3 parts of alkyl sulfate, 2 parts of lignin sulfonate and 15 parts of water-containing silica are thoroughly mixed together by grinding to give a wettable powder.

Example 2 parts of compound No. 1, 2, or 5, 3 parts of alkylaryl sulphate, 7 parts of polyoxyethylene alkylarylether, 60 parts of cyclohexanone and 20 parts of xylene are thoroughly mixed together during comminution to obtain an emulsifiable concentrate.

Example 3 parts of Compound No. 1 or 2, 1 part of water-containing silica, 35 parts of bentonite and 59 parts of kaolin are mixed well together during comminution. The resulting mixture is then kneaded with water, granulated and dried to give a granulate.

Example 4 parts of compound No. 1, 2 or 3, 0.3 parts of isopropyl phosphate, 66.7 parts of kaolin and 30 parts of talc are thoroughly mixed together during comminution to obtain a dust. Example 5 parts of compound No. 14 are mixed with 60 parts of an aqueous solution containing 3% polyoxyethylene sorbitan monoester of lauric acid and the resulting mixture is ground until the particle size of the active ingredient is less than 3 microns. 20 parts of an aqueous solution containing 3% sodium alginate as a dispersant are then added to give a suspension,

The use of the tetrahydnophthalimides of the formula I as herbicides is described in the examples below, wherein the phytotoxicity to crop plants and the herbicidal activity on weeds are evaluated as follows: The above-ground parts of the test plants are cut off and weighed (fresh weight); determining the ratio of the fresh weight of the treated plants to the untreated weight of the fresh plants, which ratio is expressed in% / o, taking as a basis the untreated weight of the untreated plants; crop damage and herbicidal activity were evaluated according to the scale shown in the following table. The nominal phytotoxicity values, 0 and 1, and the herbicidal effect values, 5 and 4, are generally considered satisfactory for the protection of crops, respectively. when weed control. The nominal values for the rice field test alone are calculated from the dry matter weight of the tested plants. ^{R The} nominal value fresh weight (in percentages of values found on the untreated parcel)

0—39 0

40—59 1—10

60—79 11— 20

80—89 21—40

90—99 41—60

100 61—100

The following control compounds are used in the test examples below: Compound No. Structural Formula Note

U.S. Patent No. 4,032,326 British Patent No. 2,046,754 A (ch ₃ ) ₂ chnh

Cl atrazine hnch ₂ ch ₃

Cl chlornitrofen η

Test Example 1

The 35 cm x 25 cm x 10 cm plastic trays are filled with topsoil and the seeds of corn, cloudberry, tomentose, sunflower, Cassia obtusifolia, bitterwort, cataract and chickweed are separately sown in the trays and left for two weeks in the hazelnut. greenhouse. The two trays were each placed in a 50 cm x 100 cm x 40 cm frame and the leaves of the test plants were sprayed from above with a given amount of test compound using a small hand syringe. After spraying, the test plants were allowed to grow for an additional 3 weeks in a greenhouse, whereupon the herbicidal activity and phytotoxicity were determined. The results are shown in Table IV. In this foliar application, the test compounds are formulated as an emulsifiable concentrate prepared according to Example 2 above and applied after dispersion in 25 ml of water with the addition of a dispersing agent. At the time of treatment, the test plants are in the 1 to 3 leaf stage and are 2 to 20 cm high.

Compound No (mass amount of active ingredient kg / ha

Table IV

phytotoxi- cita herbicidal activity of sweet corn casserole sunflower Cassia lamb's chestnut chickweed tusifolia

1 0.25 1 5 0.125 1 5 0,063 0 5 2 0.25 1 5 0.125 1 5 0,063 0 5 10 0.125 1 5 0,063 0 5 0,032 0 5 22nd 0.125 1 5 0,063 1 5 0,032 0 5 AND 1.0 3 5 0.5 3 5 0.25 2 5 0.125 1 3 (B) 10 3 5 5 2 5 2.5 2 4 1,25 0 2 C 10 0 5 5 0 3 Test Example 2 Beakers made of plastic mass with a diameter of 10 centimeters and height 10 cm se Fill the topsoil

5 5 5 5 5 5 5 5 5 4 5 4 5 4 3 5 5 5 5 5 5 5 5 5 4 4 3 5 4 3 5 5 5 5 5 5 4 5 5 4 5 4 5 3 3 5 5 5 5 5 5 4 5 5 4 4 3 5 5 3 5 4 5 5 2 5 4 5 4 1 4 3 4 3 1 2 1 3 2 0 5 4 5 5 3 5 3 4 4 2 4 2 4 3 1 3 0 2 1 0 5 2 5 5 5 5 0 4 5 5 splashes to be tested plants leave

corn seeds, hedgehogs corn feet, deaf oats, catran and tombstones are separately sown into individual beakers and allowed to grow for 2 weeks in a greenhouse. The leaves of the test plants are then sprayed with a small amount of the test compound with a small hand syringe. Growth in the greenhouse for a further 3 weeks, after which the herbicidal activity is determined. The results are shown in Table V. In this foliar application, the test compounds are formulated as an emulsifiable concentrate prepared according to the above-released Example 2 formulation and applied at a spray volume of 500 L / ha by dispersion in water with the addition of a dispersing agent.

II

Table V

compound no. dosage (amount by weight of the active ingredient j kg / ha phytotoxicity maize herbicidal activity hedgehog corns the leg oat deaf katrán mračník downy 3 0.5 1 5 5 5 5 0.125 0 1 1 5 5 4 0.5 1 5 5 5 5 0.125 0 3 3 5 5 5 0.5 1 5 5 5 5 0.125 0 4 4 5 5 6 0.5 1 5 5 5 5 0.125 0 1 2 4 5 7 0.5 0 4 4 5 5 0.125 0 2 1 3 5 8 0.5 1 5 5 5 5 0.125 1 4 4 5 5 9 0.5 1 5 5 5 5 0.125 0 5 4 5 5 10 0.5 1 5 5 5 5 0.125 1 5 5 5 5 11 0.5 0 4 3 5 5 0.125 0 3 1 4 5 12 0.5 1 5 5 5 5 0.125 1 5 5 5 5 18 0.5 1 5 5 5 5 0.125 1 2 1 4 5 19 Dec 0.5 1 5 5 5 5 0.125 0 2 2 5 5 20 May 0.5 1 5 5 5 5 0.125 0 3 3 5 5 21 0.5 1 5 5 5 5 0.125 0 2 2 5 5 22nd 0.5 1 5 5 5 5 0.125 0 3 4 5 5 23 0.5 1 5 5 5 5 0.125 1 4 5 5 5 AND 0.5 2 3 1 5 5 0.125 1 1 0 3 3 (B) 0.5 1 2 1 3 5 0.125 0 0 0 2 5

Test Example 3

Corn and broadleaf weed seeds, such as beetroot, purslane and bittergrass, are sewn in a field, pre-divided into flowerbeds, each 1 m wide. 5 leaves of the test plants from above were sprayed with a small hand syringe with a given amount of test compound formulated as an emulsifiable concentrate, prepared according to Example 2 of the formulation and dispersed in water, at a spray volume of 500 liters / ha. Herbicidal activity and phytotoxicity are determined 3 weeks after treatment of the plants. The results are shown in Table VI.

merge dosage (by weight) Table VI phytotoxicity Herbicidal activity C. amount of active ingredient), kg / ha maize Beetle purslane cabbage

1 0,063 1 5 5 5 0,032 1 5 5 4 0.016 0 5 5 3 10 0,063 2 5 5 5 0,032 1 5 5 4 0.016 1 5 5 4 13 0,063 0 5 5 4 0,032 0 4 5 3 0.016 0.125 0 4 5 2 AND 1 4 3 2 0,063 0 1 2 2 (B) 0.125 1 4 4 4 0,063 1 2 3 3

Test Example 4

The 35-cm x 25 cm-15 cm plastic hazelnuts are filled with topsoil and sowed with seeds of bitterweed, fenugreek and Cassia obtusifolia, as well as corn seeds. A given amount of test compounds formulated as a wettable powder according to Example 1 of the formulation is dispersed in water and the resulting dispersion is sprayed with a spray volume of 500 l / ha of topsoil surface. After spraying, the trays were placed in a greenhouse where the plants were allowed to grow for 20 days, whereupon herbicidal activity and phytotoxicity were determined. The results are shown in Table VII.

Table VII Compounding (weight phytotoxicity herbicidal activity nina no. Amount of active ingredient j,

kg / ha maize Cássia flood cloud tueffolia downy 4 1 0 4 5 5 0.5 0 4 4 5 5 1 0 5 5 5 0.5 0 4 4 5 6 1 0 5 4 5 0.5 0 4 4 5 7 1 0 5 4 5 0.5 0 4 4 5 8 1 0 5 4 5 0.5 0 4 4 5 9 1 1 5 4 5 0.5 0 4 4 5 11 1 0 4 4 5 0.5 0 4 4 5 12 1 0 5 4 5 0.5 0 4 4 5 AND 1 3 0 1 4 0.5 2 0 0 3 (B) 1 0 0 1 3 0.5 0 0 0 1

Test Example 5

The plastic cups of 10 cm diameter and 10 cm height are filled with topsoil and then separately sewed with corn, cotton and soybean seeds as well as binder, cloud, alfalfa, hake sorghum and greens seeds. Using a small hand-held syringe, the topsoil surface is sprayed with a given amount of test compound. After spraying, the test plants were grown for 20 days in a greenhouse, whereupon the herbicidal activity and the phytotoxicity were determined. The results are shown in Table VIII. In this pre-emergence treatment, the test compounds are formulated as emulsifiable concentrates prepared according to Example 2 of the formulation, and applied in a spray volume of 500 L / ha by dispersing in water with the addition of a dispersing agent.

Table VIII - Dose- Phytotoxicity Herbicidal Activity

security amount effectively folders), kg / ha maize cotton soybean bean povijnice mračník downy sorghum halepský Green Whites 3 1 2 2 0 5 5 5 5 0.25 1 0 0 4 5 5 4 4 1 1 0 0 4 5 5 5 0.25 0 0 0 4 '5 4 4 5 1 1 - - 4 5 5 5 0.25 0 - - 4 5 4 4 10 1 1 2 - 5 5 5 5 0.25 1 0 - 4 5 4 4 18 1 1 - 0 5 5 5 5 0.25 0 0 0 - 5 5 5 19 Dec 1 0 1 1 5 5 5 5 0.25 0 0 0 - 4 4 4 20 May 1 0 0 1 4 5 4 4 0,25, 0 0 0 - 4 4 4 21 1, 0 1 1 5 5 4 4 0.25 0 0 0 - —..... 4 4 - 22nd 1 1 2 2 5 5 5 5 0.25 0 1 0 4 5 4 4 23 1 0 - - 4 5 4 4 0.25 0 - - - 4 4 4 AND 1 2 - - 2 5 3 4 0.25 0 - - 1 4 1 1 (B) 2 1 - - 1 3 2 0 0.5 0 - - 0 1 1 0

Test Example 6

The 35 cm x 25 cm x 15 cm plastic hazelnuts are filled with topsoil and sewn with seeds of bitterwort, tombstwort, durman of cucumber, Sesbanla exaltata, Sida spinosa, Cassia obtusifolia, green feather, bloody dew and sorghum seeds, as well as seeds soy bean. A given amount of test compound, formulated as a wettable powder according to Example 1 of the formulation and dispersed in water, is sprayed onto the topsoil surface with a small hand syringe in a spray volume of 500 L / ha. After treatment, the trays were placed in a greenhouse, where the plants were allowed to grow for 20 days, whereupon phytotoxicity and herbicidal activity were determined.

The results are shown in Table IX.

compounding (mass phytotoxicity herbicidal activity nina no. amount of efficacy efficacy of durman sesbania sida cassia ober green green dew sorghum constituents) kg / ha soybean tomentose exaltata spinosa tusifolia bloody halep cucumber lq lq lq lq lq lq lq lq lq lq lq lq lq lq lq lq lq lq lq lq lq lq lq cq iq lq lq lq in lq n inininminin ^ n ic LO lW in N Tlc in lo ir nw m o lo lo in min m

LQ Φ LT Φ H O Q C ·

OOOO <Mr-) OO

CT> CO CO θ θ θ θ <M M M M M M M M M

CO 00 <ffl

Test Example 7

Seeds of maize, beet, bitterwort, tombstwort, durman of cucumber, ambrosia, cress, amaranth, bent amaranth and green scarweed are sewn in a field, pre-divided into 1 m wide beds, then divided into 3 m ² plots and these plots are sprayed with a small hand spray of given amounts of test compounds formulated as emulsifiable concentrates according to Example 2 of the formulation and dispersed in water at a spray volume of 500 L / ha. The spraying is then repeated three more times. After five weeks of plant growth, herbicidal activity and phytotoxicity were determined. The results are shown in Table X.

compounding (mass phytotoxicity herbicidal efficacy nina No of active ingredient), kg / ha Beet-root Bitter-grass Durman Ambrosia Amaranth Foxtail Green Corn Downy virgin bent cucumber

LO LO LO CO

LO LO LO

LO LO 'CM

LO LO LO CO

ΙΟ CO CO (N

LO Φ O O

Φ <□ CM rH rd O

Test Example 8

Wagner pots, each of 2 dm ² , are filled with topsoil containing broadleaf weed seeds (for example, Monochoria vaginalis, Lindernia procumbens, Rotala indica) and hedgehog seeds, and Scirpus juncoides, whereupon the topsoil is watered until the water layer height is 4 cm . Now the water-drenched topsoil is planted with the 3.5-leaf rice plant and the tuber of the rose hips. After planting, the pots are kept in a greenhouse for two days, and then a given amount of test compound formulated as an emulsifiable concentrate according to Example 2 of the formulation is pertused into the pots. Then the test plants are allowed to grow for an additional 3 weeks in a greenhouse, whereupon the herbicidal activity and the phytotoxicity are determined. The results are shown in Table XI. In this case, the emulsifiable concentrate is dispersed in water for application at a perfusion volume of 1000 liters / ha.

Table XI

compound no. dosage (amount of active ingredient by weight), kg / ha phytotoxicity rice herbicidal activity of the broadleaf hedgehog Scirpus arrow corns foot weed juncoides 1 0.25 1 5 5 5 5 0.125 0 5 5 4 4 2 0.25 1 5 5 5 5 0.125 0 4 5 4 4 3 0.25 1 5 5 4 5 0.125 1 4 5 -, 4 10 0.25 1 5 5 5 5 0.125 1 5 5 4 4 22nd 0.25 1 5 5 5 5 0.125 1 5 5 4 __ AND 0.25 1 2 5 3 0 0.125 0 Ϊ 5 2 0 (B) 0.25 0 3 5 2 0 0.125 0 1 5 1 0

Test Example 9

Wagner's pots, each with an area of 2 dm ² , are filled with topsoil and flooded with water. Three-leaf rice plants and tubers of Echleocharis acicularis and rose hips, as well as hedgehog corn seeds, Monochoria vaginalis and broadleaf weeds are seeded in the flooded water and allowed to grow for 5 days. Once the plants begin to germinate, a given amount of test compound formulated as an emulsifiable concentrate according to Example 2 of the formulation is added dropwise to the pots. The test plants were allowed to grow for a further three weeks, after which the herbicidal activity and phytotoxicity were determined. The results are shown in Table XII. Herbicidal activity is evaluated on a scale of 0 to 5. The phytotoxicity of the crops is reported according to the same rating scale as herbicidal activity.

scale growth inhibition percentage (%)

0— 9

10— 29

30—49

50— 69

70— 89

90-100

Table XII Compound Phytotoxicity Herbicidal Activity No

amount of active ingredient), kg / ha rice hedgehog Monocho- wide- leaves weed Echleo- charis acicularis arrow corns foot ria vaginalis 13 0.5 0 5 5 5 5 5 0.25 0 5 5 5 5 4 0.125 0 4 5 5 4 3 14 0.5 0 5 5 5 5 5 0.25 0 5 5 5 4 5 0.125 0 4 5 5 4 4 15 Dec 0.5 0 5 5 5 4 4 0.25 0 4 5 5 4 4 0.125 0 4 5 5 3 3 16 0.5 0 5 5 5 4 4 0.25 0 4 5 5 3 4 0.125 0 3 5 5 3 3 17 0.5 0 5 5 5 5 5 0.25 0 5 5 5 4 4 0.125 0 4 5 5 4 3 AND 1 2 4 5 5 4 3 0.5 1 3 5 5 3 3 0.25 1 1 4 4 2 2 D 1 1 4 5 5 4 3 0.5 0 3 4 5 3 1 0.25 0 2 3 4 1 0

OBJECT OF INVENTION

Claims (2)

What is claimed is: 1. A herbicidal composition comprising as active ingredient X represents a chlorine atom or a bromine atom and R represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 3 to 4 carbon atoms or an alkynyl group having 3 to 4 carbon atoms, together with an inert carrier. 2. A process for the preparation of a compound of formula (I) contained as an active ingredient in a herbicidal composition according to claim 1, characterized in that the compound of formula (III) X is as defined in item 1, reacted with a halide of formula R - Y, where R is as defined in 1 and Y is chlorine, bromine or iodine in the presence of a base.