CS227022B2 - Herbicide - Google Patents

Abstract

2-cyanoacrylic acid esters of formula (I) are new (where R1 is Me, CF3, Cl or Br; R2 is Cl,Br,I or methylsulphonyl; R3 is H,Cl or Br, or R3 is 5-MeO, in which case R1 and R2 are Cl and R2 is H if R3 is 3-Cl; R4 is 1-3C alkyl, allyl or propargyl). (I) are strong and selective herbicides. Specifically claimed cpds. (I) are 2'-(2,4,6-trichlorophenyl)-hydrazino -2-cyanoacrylic acid methyl ester (Ia) and 2'-(2,4-dichlorophenyl) hydrazino-2-cyano-acrylic acid methyl ester.

Description

The present invention relates to a herbicidal composition comprising as active ingredient the novel 5-amino-1-phenylpyrazole-4-carboxylic acid esters. The invention further relates to a process for the production of these compounds, as well as to their use for combating undesirable plant growth.

Esters of 5-amino-1-phenylpyrazole-4-carboxylic acid containing a chlorine atom in the phenyl moiety are known in the literature [cf. U.S. Patent 3,567,735; Archive Pharm. 312 (1979) 703). These substances serve as. intermediates, for example, for the synthesis of diuretics or compounds having antibacterial activity. Nothing is known about the herbicidal properties of these compounds.

It has now been found that 5-amino-1-phenylpyrazole-4-carboxylic acid esters of the general formula I in which:

^R1 represents a methyl group, ·, chlorine or bromine,

R2 is chlorine or bromine,

R 3 represents hydrogen, chlorine or bromine;

R 4 represents an alkyl group having 1 to 3 carbon atoms, surprisingly having potent and at the same time selective herbicidal effects.

The present invention relates to a herbicidal composition, characterized in that it contains at least one 5-amino-1-phenylpyrazole-4-carboxylic acid ester of the aforementioned general formula (I) together with an active ingredient. inert carrier.

5'-Amino-1-phenylpyrazole-4-carboxylic acid esters of formula (I) are obtained, for example, by reacting substituted phenylhydrazines of formula (II)

in which

R 1, R ² and R ³ have the meanings given above, with the substituted 2-cyanoacrylic acid esters of formula III

HCN \ Z

C = C

R ⁵ - ^ СОгИ 'in which

R ⁴ has the above vvýznam and

R5 is alkoxy having 1 to 4 carbon atoms or Ν, Ν-dialkylamino having 1 to 4 carbon atoms in the alkylamino or hydroxy group is, 'to form an ester substituted ² --enyllhydrazino 2-cyanoacrylic ester of the formula IV

in which

R1, R2, R3 and R4 have the above meanings, at temperatures below 70 ° C (first stage) and these intermediates are cyclized in the second stage by heating to temperatures above 70 ° C (procedure A) or by treatment with an aqueous mineral acid at temperatures between 0 ° C and 150 ° C, preferably between 20 ° C and 100 ° C (Procedure B).

Such as solvents for the process. Especially suitable are alcohols such as methanol, ethanol, but ethers such as dioxane, tetrahydrofuran, anisole can also be used. or. hydrocarbons such as toluene and xylene. After completion of the reaction in the first or second step, the solution is cooled and the product is isolated by filtration and optionally purified by recrystallization. When cyclization according to procedure B is carried out using an aqueous mineral acid, preferably 5 to 38%. % by weight of hydrochloric acid. or 5 to 50% sulfuric acid, then the reaction mixture after the reaction is complete. it is diluted with two to twenty times the volume of water and the cyclization product is filtered off and washed with neutral alkali or ammonia until neutral and optionally recrystallized.

Further, 5-amino-1-phenylpyrazole-4-carboxylic acid esters of formula I are obtained by reaction of substituted phenylhydrazines of formula. II with substituted 2-cyanoacrylic acid esters of formula III in the first step at temperatures above 70 ° C (procedure C). Suitable solvents are those used in process A, preferably alcohols whose boiling points are above 70 ° C. The isolation of the reaction products is carried out as described in Procedure A. 2-Cyanoacrylic esters of formula III are used in at least a molar amount, based on the substituted phenylhydrazines of formula II, preferably in stoichiometric amounts. If process A or C is used instead of the free phenylhydrazines of formula II, their salts with mineral acids such as hydrochlorides or sulphates, it is expedient to release the substituted phenylhydrazine of formula II 'first by adding an equivalent amount of alkali metal alkoxides or sodium acetate and then reaction.

The phenylhydrazines II used are known or can be prepared according to known methods (Methoden der Organ. Chemie, Houben. Weyl, Vol. 10/2, p. 180 et seq.). The 2-cyanoacrylic acid esters of formula III used are known [cf. DCS 2,635,841; Chem. Ber. 51964) 97, 3397).

The 2‘-phenylhydrazine-2-cyanoacrylic acid esters of formula IV isolated in carrying out process A also have herbicidal properties. The following examples illustrate the production of intermediates. .and end products.

In the examples, the parts by weight are relative to parts by volume in a ratio of kg / liter.

Preparation of 2‘-phenylhydrazino-2-cyanoacrylic acid esters of formula IV ..., .....

Example A

148.1 parts by weight of 2,4,6-trichlorophenylhydrazine is added to a solution of 108.5 parts by weight of ethoxymethylene-2-cyanoacetic acid methyl ester in 1000 parts by volume of methanol. From this solution,. A crystalline slurry precipitated which, after stirring for 3 hours, filtered and dried in vacuo at. temperature. 40 ° C provides 187.4 parts by weight of 2- (2,4,6-trichlorophenyl) hydrazino-2-cyanoacetate methyl ester. 174 DEG-175 DEG.

For C11H8Cl3N3O2 (molecular weight 320.5) calculated:

41.22% C, 2.52. % H, 13.11. % N,

П O7QH O *

40.9% C, 2.8% H, 12.8% N.

Example B

A suspension of 21.4 parts by weight of 2,4-dichlorophenylhydrazine hydrochloride in 150 parts by volume of methanol is neutralized by the addition of about 18 parts by weight of a 30% sodium ethoxide solution and 15.5 parts by weight of ethoxymethylene-4-cyanoacetate methyl ester. The reaction mixture was stirred at 25 ° C for 3 hours and then heated at reflux for 15 minutes. From the filtrate, 17.5 parts by weight of 2 '- (2,4-dichlorophenyl) -hydrazino-2-cyanoacrylic acid methyl ester of melting point are isolated by evaporation of me227022 thanol in vacuo and after recrystallization from ethanol (at 50 ° C). Mp 154-156 ° C.

For C11H9Cl2N3O2 (molecular weight 286) calculated:

% C, 46.18;% H, 3.17;% N, 14.69.

H, 3.2; N, 14.8.

Accordingly, the following 2‘-phenylhydrazino-2-cyanoacrylic acid esters of formula IV can be produced:

R ¹ R2 R ³ R ⁴ 1.1. Cl Cl H C2H5 175 Cl Cl 6-C1 C2H5 166 Cl Cl 6-C1 I-C3H7 130 СНз Cl H СНз 140 Br Br 6-Br СНз 182 Cl Br 5-C1 СНз Cl Cl 5-C1 СНз 195 СНз Br H СНз СНз Br 6-Br СНз СНз Cl 6-C1 СНз Cl Cl 6-Br СНз Cl Br 6-Br СНз Cl Br 6-C1 СНз Br Cl 6-Br СНз Br Br H СНз

Example 1 (Procedure B)

90.0 parts by weight of methyl ester 2‘-

- (2,4,6-Trichlorophenyl) hydrazino-2-cyanoacrylic acid was stirred in 300 parts by volume of 18% hydrochloric acid at 80 ° C for 5 hours. After cooling and diluting with 500 parts by volume of water, 70.6 parts by weight of 5-amino-1-methyl-methyl ester are isolated after suction and washed with water and sodium bicarbonate solution until neutral.

- (2,4,6-trichlorophenyl) pyrazole-4-carboxylic acid, m.p. 179-180 ° C (active ingredient no. 1).

For C11H8Cl3N3O2 (molecular weight 320.5) calculated:

% C, 41.22;% H, 2.52;% N, 13.11.

C 41.4%, H 2.8%, N 13.6%

EXAMPLE 2 5-Amino-1- (2,4-dichlorophenyl) pyrazole-4-carboxylic acid methyl ester, m.p. 143 DEG-145 DEG C. (active substance No. 2).

For C11H9Cl2N3O2 (molecular weight 286) calculated:

% C, 46.18;% H, 3.17;% N, 14.69;

C, 46.2; H, 3.2; N, 14.7.

Example 3 (Procedure A)

45.0 parts by weight of 2‘- (2,4-dichlorophenyl) hydrazino-2-cyanoacrylic acid methyl ester was heated to 200 parts by volume of n-propanol for 6 hours at reflux. After cooling, 34.6 parts by weight of 5-amino-1- (2,4-dichlorophenyl) pyrazole-4-carboxylic acid methyl ester of melting point 144 DEG-145 DEG C. (active substance No. 2) are isolated by suction.

(procedure В)

Example 4

15.0 parts by weight of 2- (2,4-dichlorophenyl) hydrazino-2-cyanoacrylic acid methyl ester is stirred in 50 parts by volume of concentrated hydrochloric acid for 12 hours at 25 ° C and then stirred in 500 parts by volume of ice water. The precipitate formed after filtration and washing with water and sodium bicarbonate solution gave a neutral reaction of 14.2 parts (procedure C).

21.2 parts by weight of 2,4,6-trichlorophenylhydrazine and 15.5 parts by weight of ethoxymethylene-2-cyanoacetic acid methyl ester are heated to 120 parts by volume of n-butanol under reflux for 2 hours. After cooling, 22.8 parts by weight of 222222 were isolated by suction

The following compounds of formula I were prepared in an analogous manner to that described in the above examples:

5-Amino-1- (2,4,6-trichlorophenyl) pyrazole-4-carboxylic acid methyl ester, m.p. 180-181 ° C. (Active substance No 1).

number Ri R2 R3 R ⁴ melting point (° С) 3 Cl Cl H C2H5 109 4 Cl Cl 6-C1 C2H5 105 5 Cl Cl 6-C1 1-C3H7 152 6 СНз Cl H СНз 109 7 Br Br 6-Br СНз 194 8 Cl Br 5-C1 СНз 173 9 Cl Cl 5-C1 СНз 175 10 СНз Br H СНз 123 11 СНз Br 6-Br СНз 175 12 СНз Cl 6-C1 СНз 13 Cl Cl 6-Br СНз 199 14 Cl Br 6-Br СНз 208 15 Dec Cl Br 6-C1 СНз 16 Br Cl 6-Br СНз 172 17 Br Br H СНз 19 Dec Cl Br 6-C1 СНз 22nd Cl Cl 6-CI п-СзН7

The use as herbicides takes place, for example, in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scatters, granulates, by spraying, fogging, dusting, spreading or potting. The use forms depend entirely on the intended use. In any case, these forms are intended to ensure the finest possible distribution of the new active substances.

For the production of directly sprayable solutions, emulsions, pastes and oil dispersions, mineral-to-high-boiling mineral oil fractions, such as kerosene or oil for diesel engines, tar oils, etc., oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or derivatives thereof such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone etc. strongly polar solvents such as dimethylformamide ,. dimethylsulfoxide, N-methylpyrrolidone, water, etc.

Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders, oil dispersions by adding water. For the production of emulsions, pastes or oil dispersions, the substances as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersing agents or emulsifiers. Concentrates consisting of the active ingredient, wetting agent, adhesive, dispersant or emulsifier and, optionally, solvent or oil, which are suitable for dilution with water, may also be prepared.

Herbicides contain, for example, 5 to 95% by weight of active ingredient, in particular 10 to 80% by weight of active ingredient.

Surfactants include: ligninsulfonic acid salts, naphthalenesulfonic acids, alkali metal phenolsulfonic acids, alkaline earth metals or ammonium or ammonium salts, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, alkali metal dibutylnaphthalenesulfonic acid salts, and alkaline earth metal salts of lauryl ether sulfates , sulphated fatty alcohols, alkali metal and alkaline earth metal fatty acid salts, sulphated hexadecanols, heptadecanols, octadecanolides, sulphated fatty alcohol glycol ether salts, condensation products of sulfonated naphthalene and derivatives of naphthalene with formaldehyde, condensation products of naphthalene and naphthalene formaldehyde, polyoxyethylenoctylphenol ethers, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylarylpolyl ether alcohols, isotridecyl alcohol, condensation produ ethylene oxide fatty acid esters, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulphite waste liquors and methylcellulose.

Powders, dusts and dusts can be prepared by mixing or comminuting the active ingredients with a solid carrier.

Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solid carrier materials are, for example, mineral clays such as silicas, silicates, talc, kaolin, lime, ore, loess, clay, dolomite, diatomaceous earth, calcium sulfate and magnesium sulfate, magnesium oxide, ground plastics, binders such as ammonium sulfate, phosphate ammonium, ammonium nitrate, urea and plant products such as cereal flour, tree bark flour, wood flour and ground nut shells, powdered cellulose and other solid carriers.

Examples explaining the composition and preparation of devices:

Example and parts of compound No. 1 are mixed with 10 parts by weight of N-methyl-za-pyrrolidone to give a solution which is suitable for application in the form of small drops.

Example b parts by weight of Compound No. 1 are dissolved in a mixture consisting of 80 parts by weight of xylene, 6 parts by weight of the addition product of 8 to 10 moles of ethylene oxide with 1 mol of N-monoethanolamide-oleic acid, 2 parts by weight calcium-dodecylbenzenesulfonic acid; 2 parts by weight of the addition product of 40 moles of ethylene oxide with 1 mole of castor oil.

Example c parts by weight of Compound No. 1 is dissolved in a mixture consisting of 60 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 5 parts by weight of the addition product of 7 moles of ethylene oxide with 1 mol of isooctylphenol and 5 parts by weight of the addition product of 40 moles of ethylene oxide. mol of castor oil.

Example d parts by weight of Compound No. 1 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction, boiling point 210-180 ° C, and 10 parts by weight of 40 mol-ethylene oxide addition product. 1 mol of castor oil.

Example e parts by weight of the active substance No. 1 are well mixed with 3 parts by weight of diisobutylnaphthalene-α-sulfonic acid sodium salt, 10 parts by weight of ligninsulphonic acid sodium salt from sulphite waste liquors and 7 parts by weight of powdered silica gel and milled on a hammer mill .

Example f parts by weight of Compound No. 1 is intimately mixed with -95 parts by weight of finely dispersed kaolin. In this way, a dust is obtained which contains 5% by weight of the active ingredient.

Example g

30% by weight of Compound (1) is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of the silica gel. In this way, an effective composition with good adhesion is obtained.

Example h parts by weight of the active substance No. 1 is intimately mixed with 10 parts of sodium salt of the condensation product of phenolsulfonic acid, urea and formaldehyde, 2 parts of silica gel and 48 parts of water. In this way a stable aqueous dispersion is obtained. Dilution with 100,000 parts by weight of water gives an aqueous dispersion containing 0.04% by weight of the active ingredient.

Example 1 parts of active ingredient No. 1 are intimately mixed with 12 parts of calcium dodecylbenzenesulfonic acid, 8 parts of polyglycol ether of fatty alcohol, 2 parts of sodium condensation product of phenolsulfonic acid, urea and formaldehyde and 68 parts of paraffinic mineral oil. In this way a stable oil dispersion is obtained.

The influence of various representatives of the new 5-amino-1-phenylpyrazole-4-carboxylic acid esters on the growth of desired and undesirable plants was investigated by the following experiments carried out in a greenhouse:

As containers - for the cultivation - of the cultures, pots of 300 milliliters were filled with clay sand filled with about 1.5% humus as a substrate. - Seeds of the test plants were sown by - species on the soil surface. The pre-emergence treatment of the application of the active compounds to the soil surface was carried out immediately. The active substances were suspended or emulsified in water - as a dispersing medium - and sprayed by means of finely dispersed nozzles. An amount of active compound corresponding to 3.0 kg of active compound / ha was used. After application, the containers are gently irrigated to achieve germination and plant growth. The containers were then covered with a transparent plastic sheet and left covered until the plants began to grow. This covering causes uniform germination of the test plants, if not yet affected by the active substances. For the purposes of post-emergence treatment, the test plants are grown according to the growth form up to a height of 3 to 10 cm, before the treatment is carried out.

For post - emergence treatment, either directly sown and grown plants in the same containers or. these plants are cultivated separately as seedlings and transplanted into experimental containers only a few days before treatment. It should be noted that in the rice used in postemergence experiments, the substrate was enriched with peat. · The same applies to Galium · aparine (bedstraw). The application rate for post-emergence treatment is 0.5 kg of active substance / ha of pro-compound No. 1, 2, 6, 7.

Dose 1,0 kg · effective. / ha was used for compound 8. 5-Amino-1- (4-chlorophenylpyrazole) -4-carboxylic acid methyl ester (Aj, although known as a substance but not yet described as a herbicide, and · here used as a comparative agent, is used in an amount of 2.0 kg / ha for post-emergence application 2'-phenylhydrazino-2-cyanoacrylic acid esters (Example A, Example B) with herbicidal properties used to The 5-amino-1-phenylpyrazole-4-carboxylic acid esters were used in an amount of 3.0 kg of active ingredient / ha, both in pre-emergence and post-emergence treatments.

In the post-emergence treatment, the covering of the plastic foils is generally not carried out. The pots are placed in a greenhouse, with parts of the greenhouse where the temperature is selected for thermophilic plant species. higher (20 to 35 ° C), and for plants that are milder in climate, those parts of the greenhouse are selected where · the temperature is from 15 to 25 ° C. The duration of the experiment is 2 to 3 weeks. During this time, plants are treated and their response to individual treatments evaluated. The evaluation is carried out on a scale from 0 to 100. In doing so. · Means 0, no damage, or · represents normal growth, and · 100 · means that the plants do not appear at all, or that they are · completely · destroyed at least above-ground parts. · Plants.

the results show that they show compounds 1, 2, 3, 4, 6 and 7 in a greenhouse for pre-emergence treatment and 3 kg. active substance / ha and remarkable herbicidal effect.

Further, the greenhouse experiments show that the active compounds of Example A and Example B applied at 3.0 kg / ha have a good herbieidic effect in pre-and post-emergence application.

In these greenhouse experiments, Compounds No. 1, 2, 6 and 7 applied an amount of 0.5 kg of active ingredient / ha and a very good and broad effect against numerous dicotyledonous undesirable plants. Cereal types such as winter wheat are largely protected or only temporarily damaged.

As a further result of these greenhouse experiments, the result obtained with Compound No. 8 applied post-emergence at 1.0 kg of active substance / ha. This compound is herbicidally effective against several dicotyledonous weeds. without damaging or to a greater extent.

Known Compound A used as. the comparative compound was applied postemergently at 2.0 kg of active ingredient / ha and showed no remarkable herbicidal activity.

Furthermore, in the described greenhouse experiments, · postemergence application · 0.5 · kg of active substance No. 13 / ha · it was found that this compound has a very good herbieid effect against dicotyledonous weeds without damaging cereal species. In the same way, it combines compound 16 in the same experiments using 1.0 kg of active substance / ha of dicotyledonous weeds, with only slight and temporary damage to the cereals.

If certain crop plants are somewhat more susceptible to the active ingredients in leaf treatment, then application techniques may also be used in which the herbicidal compositions are sprayed so that the leaves of the more sensitive crop plants are not The possibility of being wetted by these means, whereby. they spray the leaves of the undesirable plants that grow under these crop plants or spray the uncovered soil surface below the plants (post-directed, lay-by).

Due to the versatility of the application methods, the herbicides according to the invention can be used to eliminate undesirable plant growth even in a much larger number of crop plants. The application rates can vary between 0.1 and 15 kg of active ingredient / ha and more.

For example, the following crop plants are suitable:

botanical name Czech name Allium сера onion Pineapple comusus pineapple Arachis hypogaea peanut Asparagus officinalis asparagus Avena sativa oats Beta vulgaris spec, altissima sugar beet Beta vulgaris spp. rapa fodder beet Beta vulgaris spp. esculenta beetroot Brassica napus var. napus rape Brassica napus var. napobrassica turnip Brassica napus var. rapa white beets Brassica rapa var. silvestris oilseed rape Camellia sinensis tea Carthamus tinctorius Safflower Carya illinoinensis walnut pecan Citrus limon lemon tree Citrus maxima lemon tree Citrus reticulata tangerine Citrus sinensis orange Coffea arabica (Coffea canephora (Coffea liberica) coffee tree Cucumis melo melon Cucumis sativus cucumber Cynodon dactylon troskut Daucus carota carrot Elaeis guineensis coconut tree Fragaria vesca Strawberry Glycine max soya Gossypium hirsutum cotton (Gossypium arboreum cotton Gossypium herbaceum cotton Gossypium vitifolium) cotton Helianthus annuus sunflower Helianthus tuberosus Jerusalem artichoke Hevea brasiliensis rubber tree Hordeum vulgare barley Humulus lupulus hop Ipomoea batatas sweet potato Juglans regia Walnut Lactuca sativa salad Lens culinaris edible lentils Linum usitatissimum only Lycopersicon lycopersicum tomato Malus spp. apple tree Manihot esculenta tapioca Medicago sativa lucerne Mentha piperita peppermint Musa spp. banana tree Nicotiana tabacum (N. rustica) tobacco Olea europaea olive Oryza sativa rice Panicum miliaceum millet Phaseolus lunatus bean Phaseolus mungo - Phaseolus vulgaris shrimp beans Pennisetum glaucum Petroselinum crispum spp. tuberosum parsley root Picea abies spruce Abies alba silver fir Pinus spp. pine Pisum sativum pea Prunus avium cherry Prunus domestica plum Prunus dulcis almond

botanical name

Prunus persica

Pyrus communis

Rlbes sylvestre

Ribes uva-crispa

Ricinus communis

Saccharum officinarum

Secale cereale

Sesamum indicum

Solar tuberosum

Sorghum bicolor (p. Vulgare)

Sorghum dochna

Spinacia oleracea Theobroma cacao

Trifolium pratense

Triticum aestivum

Vaccinium corymbosum species Vaccinium vitis-idaea Vicia faba

Vigna sinensis (V. unguiculata) - Vitis vinifera

Zea mays English name peach pear pear currant red gooseberry castor sugar cane rye sesam potatoes sorghum bicolored sorghum spinach. cocoa clover wheat blueberries cranberries bob horse bean grape corn

In order to broaden the spectrum of activity and to achieve synergistic effects, the novel 5-amino-1-phenylpyrazole-4-carboxylic acid esters of the formula I can be mixed with numerous representatives of other groups of herbicidally active or growth-regulating active substances and applied together. For example, diazines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dimtroaniline, N-phenylcarbamates, thiolcarbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, thiophenes, uracil, benzofuran derivatives, cyclohexane-1,3-dione derivatives and others.

A number of active substances which, together with the novel compounds, offer mixtures suitable for a wide variety of applications, are given by way of example below:

5-amino-4-chloro-2-phenyl-3 (2H) -pyridazinone,

5-amino-4-bromo-2-phenyl-3 (2H) -pyridazinone,

5-amino-4-chloro-2-cyclohexyl-3 (2H) -pyridazinone,

5-amino-4-bromo-2-cyclohexyl-3 (2H) -pyridazinone;

5-methylamino-4-chloro-2- (3-difluoromethylphenyl) -3- (2H) -pyridazinone,

5-methylamino-4-chloro-2- (3-α, α, β, β-tetrafluoroethoxyphenyl) -3 (2H) -pyridazinone,

5-dimethylamino-4-chloro-2-phenyl-3 (2H) -pyridazinone,

4,5-dimerhoxy-2-phenyl-3 (2H) -pyridazinone,

4,5-dimethoxy-2-cyclohexyl-3 (2H) -pyridazinone,

4,5-dimethoxy-2 '(3-trifluoromethylphenyl) -3 [2H] -pyridazinone,

5-Methoxy-4-chloro-2- (3-trifluoromethyl-phenyl) -3 (2H) -pyridazinone,

5-amino-4-bromo-2 (3-methylphenyl) -3 (2H) -pyridazinone,

3 - ((-methylethyl-1H-2,2,1,3-benzo-hiadiazin-4 (3H) -ont-2,2-dloxide and its salts),

3 - ((.-Methylethyl) -8-chloro-1H-2,1,3-benzothiadiazine-4 (3H) -one-2,2-dioxide and its salts,

3- ((-methylethyl) -8-fluoro-1H-2,1,3-benzothiadiazine-4 (3H) -tont-2,2-dioxide and its salts,

3- ((-methylethyl) -8-piperidin-1Η-2,13-benzothiadiazine-4 (3H) -one 2,2-dioxide and its salts, 1-methoxymethyl-3- (1-methoxyl) -3- (1-methoxyl) -2- 1,3-benzothiadiazine-4 (3H) -one 2,2-dioxide, 1-meroxymethyl-8-chloro-3t (1-methylothyl) -1,2,3-benzothiadiazine-4 (3-) -one-2,2-dioxide 1-Methoxymethyl-8-fluoro-3- (tert-ethyl) -2,1,3-benzothiadiazin-4 (3H) -one 2,2-dioxide, 1-cyano-8-chloro-3- [1-methylethyl) -2,1,3-benzothiadiazin-4 (3H) -one-2,2-dioxide, 1-cyano-8-fluoro-3- (1-methylethyl) -2,1,3- benzothiadiazin-4 (3H) -one-2,2-dioxide, 1-cyano-8-methyl-3- (1-methylethyl) -2,1,3-benzothiadiazin-4 (3H) -one-2,2- Dioxide, 1-cyano-3- (1-methylethyl) -2,1,3-benzothiadiazin-4 (3H) -one 2,2-dioxide,

1-azidomethyl-3- (1-methylethyl) -2,1,3-benzothiadiazin-4 (3H) -one 2,2-dioxide,

3- (1-methylethyl) -1H-pyridino [3,2-e] -2,1,3-thiadiazin-4-one 2,2-dioxide,

N- (1-ethylpropyl) -2,6-dinitro-3,4-dimethylaniline,

N- (1-methylethyl) -N-ethyl-2,6-dinitro-4-trifluoromethylaniline,

N-n-propyl-N- (3-chloroethyl-2,6-dinitro-4-trifluoromethylaniline),

N-n-propyl-N-cyclopropylmethyl-2,6-dinitro-4-trifluoromethylaniline,

N-bis (n-propyl) -2,6-dinitro-3-amino-4-trifluoromethylaniline,

N-bis (n-propyl) -2,6-dinitro-4-methylaniline,

N-bis (n-propyl) -2,6-dinitro-4-methylsulfonylaniline,

N-bis (n-propyl) -2,6-dinitro-4-aminosulfonylaniline, bis (β-chloroethyl) -2,6-dinitro-4-methylaniline,

N-ethyl-N- (2-methylallyl) -2,6-dinitro-4-trifluoromethylaniline,

N-methylcarbamic acid 3,4-dichlorobenzyl ester,

N-methylcarbamic acid 2,6-di- (tert-butyl) -4-methylphenyl ester, N-phenylcarbamic acid isopropyl ester,

N-3-chlorophenylcarbamic acid 3-methoxy-2-propyl ester, N-3-chlorophenylcarbamic acid isopropyl ester, N-3-chlorophenylcarbamic acid 1-butin-3-yl ester,

N-3-chlorophenylcarbamic acid 4-chloro-2-butin-1-yl ester, N-3,4-dichlorophenylcarbamic acid methyl ester, N- [4-aminobenzenesulfonyl) carbamic acid methyl ester,

O- (N-phenylcarbamoyl) propanone oxime,

N-ethyl-2- (phenylcarbamoyl) oxypropionamide

3'-N-isopropylcarbamoyloxy-propionanilide, ethyl N- [3- (N'-phenylcarbamoyloxy] phenyl] carbamate, methyl N- [3- (N'-methyl-N'-phenylcarbamoyloxy) phenyl] carbamate, isopropyl N- [3- (N'-ethyl-N'-phenylcarbamoyloxy) phenyl] carbamate, methyl N- [3- (N'-3-methylphenylcarbamoyloxy) phenyl] carbamate, methyl N- [3- (N'-4-fluorophenylcarbamoyloxy) phenyl] carbamate, methyl N- [3- (N'-3-chloro-4-fluorophenylcarbamoyloxy) phenyl] carbamate, methyl-N-dichlorofluoromethylsulfenyl-

- [3- (N‘-dichlorofluoromethylsulfenyl-N‘-phenylcarbamoyloxy) phenyl] carbamate, methyl N-dichlorofluoromethylsulfenyl-

- [3- (N'-dichloromethylsulfenyl-N'-3-methylphenylcarbamoyloxy) phenyl] carbamate, ethyl N- [3- (N'-3-chloro-4-fluorophenylcarbamoyloxy] phenyl] carbamate, ethyl N- [3- (N'-3,4-difluorophenylcarbamoyloxy) phenyl] carbamate, methyl N- [3- (N'-3,4-difluorophenylcarbamoyloxy) phenyl] carbamate, N-3- (4-f-methyl ester) N-3- (2-methylphenoxycarbonylamino) phenylcarbamic acid ethyl ester, N-3- (4-fluorophenoxycarbamic acid methyl ester) N-3- (4-fluorophenoxycarbamic acid methyl ester), N- (3- (2,4,5-trimethylphenoxycarbonylamino) phenyl ester) acids, N- (3- (phenoxycarbonylamino) phenylthiolcarbamic acid methyl ester), N, N-diethylthiolcarbamic acid p-chlorobenzyl ester, N, N-di- (n-propyl) thiolcarbamic acid ethyl ester, N, N-di- (n-propyl ester) -propyl) thiolcarbamic acids,

2,3-N, N-diisopropylthiolcarbamic acid dichloro-ester,

2.3.3- N, N-diisopropylthiolcarbamic acid trichlorallyl ester,

N, N-diisopropylthiolcarbamic acid 3-methyl-5-isoxazolylmethyl ester,

N, N-diisopropylthiolcarbamic acid 3-ethyl-5-isoxazolylmethyl ester, N, N-di-sec-butyl-thiolcarbamic acid ethyl ester, N, N-di-sec-butyl-thiolcarbamic acid benzyl ester, N-ethyl-N-cyclohexylthiolcarbamic acid ethyl ester acids, N-ethyl-N-bicyclo [2,1,1] heptylthiolcarbamic acid ethyl ester,

S- (2,3-di chlorallyl) - (2,2,4-trimethylazetidine) -1-carbothiolate,

S- (2,3,3-trichlorallyl) - (2,2,4-trimethylazetidine) -1-carbothiolate,

S-ethyl-hexahydro-1H-azepine-1-carbothiolate,

S-benzyl- (3-methylhexahydro-1H-azepine) -1-carbothiolate,

S-benzyl- (2,3-dimethylhexahydro-1H-azepine) -1-carbothiolate,

N-ethyl-N-n-butylthiolcarbamic acid S-ethyl- (3-methylhexahydro-1H-azepine) -1-carbothiolate,

2-chlorallyl ester of N, N-dimethyl-dithiocarbamic acid, sodium salt of N-methyl-dithiocarbamic acid, sodium salt of trichloroacetic acid, sodium salt of α-dichloropropionic acid, sodium salt of α, α-dichlorobutyric acid, sodium salt of α, ial, N, N -tetrafluoropropionic acid, sodium α-methyl-α, β-dichloropropionic acid, α-chloro-β- (4-chlorophenyl) propionic acid methyl ester, α, β-dichloro-β-phenylpropionic acid methyl ester, benzamidooxyacetic acid,

2.3.5- triiodo-benzoic acid and its salts, esters and amides,

2.3.6- trichlorobenzoic acid and its salts, esters and amides,

2.3.5.6- tetrachlorobenzoic acid and its salts, esters and amides,

2-methoxy-3,6-dichlorobenzoic acid and its salts, esters and amides,

2-methoxy-3,5,6-trichlorobenzoic acid and its salts, esters and amides,

3-amino-2,5,6-trichlorobenzoic acid and its salts, esters and amides,

O, S-dimethyl-tetrachlorothioterephthalate, dimethyl-2,3,5,6'-tetrachloro-terephthalate, disodium 3,6-endoxohexahydrophthalate,

4-amino-3,5,6-trichloropicolinic acid and its salts, 2-cyano-3- (N-methyl-N-phenylamino) -acrylic acid ethyl ester, 2- [4- [4'-chlorophenoxy) phenoxy] propionic acid isobutyl ester, 2- [4- (2 ', 4'-dichlorophenoxy) phenoxy] propionic acid methyl ester, 2- [4- (4'-trifluoromethylphenoxy) phenoxy] propionic acid methyl ester, 2- [4- (2'-chloro'-) -, 4'-trifluorophenoxy) phenoxy] propionic acid, sodium salt. 2- [4- (3 ', 5'-dichloropyrid-2-yloxy) phenoxy] propionic acid, 2- (N-benzoyl-3,4-dichlorophenylamino) propionic acid ethyl ester, 2- (N-benzoyl-3) methyl ester -chloro-4-fluorophenylamino) propionic acid, 2- (N-benzoyl-3-chloro-4-fluorophenylamino) propionic acid isopropyl ester, 4- (4'-thiifluoroethylphenoxy) pentene-2-carboxylic acid ethyl ester,

C-chloro-e-ethalamino-6-isopropylamino-1,3,5-triazine,

2-chloro-3-4-d-halo-6- (amino-2'-propionitrile) -1,3,5-triazine,

2-cdloro-4-ethylamino-6- (2-methoxypropyl) -2-amino-1,3,5-triazine,

2-Cdloro-4-ethylamino-6-butin-1-yl-2- (4-chloro-3,5-triazine),

2-cdloro-4,6-bisetdylamino-1,3,5-triazine,

2-chloro-4,6-bisisopropylamino-1,3,5-. -triazine,

2-chloro-4-isopropylamino-6-cyclopropylamino-1,3,5-triazine,

2-azido-4-methyl-amino-6-isopropyl-. · Amino-1,3,5-triazine _i

2-methylthio-4-ethylamino-6-isopropylamino-1S-triazole;

2-methylthio-4-ethylamino-6-tert-butylamino-1,3,5-triazine,

2-methylthio-4,6-bisethylamino-1,3,5-triazine,

2-Methylthio-4,6-bisisopropylamino-1,3,5-triazine

2-methoxy-4-ethylamino-6-isopropylamino-1,3,5-triazine,

2-methoxy-4,6-bisethylamino-1,3,5-triazine,

2-methoxy-4,6-bisisopropylamino-1,3,5-triazine,

4-amino-6-l-tert-butyl-3-methylthio-5,5-α-1,2,4-thiazin-5-one,

4-Amino-6-methyl-1-methyl-1,2,4-triazin-1,2,4-triazin-5-one;

4-Sobulyl-denamm 6-6-tert-butyl-3-methylthio-4,5-didydro-1,2,4-thiazin-5-one,

MethyllУ 1-cyclohexyl-6-dimethyl-minOll, У, _{5ltriazin-2) 4ldion)}

U-chloro-C-chloro-3-indlyluracil,

У-terr.bУlyl-rl0rзm-3-mdthyluiacil

У - sooropyllrlbззm-3-π-thyluracil,

3-sebyl-rl0ззm-3-mdthyluiacil,

3- (2-methyl-3-methyluracil)

3- ((-te-ahddripynyl) -5,5-ϊ3ππ3-υιυlenuracil,

C-cyclohexy-6, β-thiazimide-hyeniacil,

2-Methyl-4- (3'-trifluoromethylphenyl) tetrazahydazole, 2,4-oxadiazine-3,5-dione,

2-Methyl-4- [4'-fluorophenyl) tetradydro-1,2,4-oxadiazine-5,5-dione,

Ω-amino-1,2,4-triazole, 1-allyloxy-1- (4-bromophenyl) -2- [1‘, 2‘, 4‘-thiazol-1'-yl] ethane and its salts,

1- (4-cyano-phenoxy) -3,3-dimethyl-ethyl-1-

- (0H-1,2,2U [thiaziazol-1-yl] butan-2-one,

N, N-diallylchloroacetamide,

N-isopropyl-2-chloroacetanilide,

N- (1-butyr-1-yl) -2-chloroacetanilide,

2-Methyl-6-ethyl-N-β-paraargyl-2-cdloroacetanilide

2-Methyl-6-etdyl-N-ethoxymethyl-2-cdloroacetanilide,

2-Methyl-6-ethyl-N- (2-metdoxy-1-methyl-ethyl) -2-chloroacetanilide,

2-Methyl-3-ethyl-N- (isopropoxycarbonylethyl) chloroacetanilide,

2-methyl-6-ethyl-N- [4-methoxy-pyrazol-1-ylmethyl) -2-chloroacetamide,

2-Methyl-6-methyl-N '(1-pyrazcoylmethyl) -

2,6-e.imeth81-N- (1-pyrazo-γ-methyl) -2-chloroacetanilide,

2,6-dimethyl-N- (4-methylpyrazol-1-ylmethyl) -2-chloroacetanilide,

2,6-Dimethyl-N- (1,2,4-riazol-11-ylmethyl) -1-chloroacetanilide

2,6-dimethyl-N- (η 5-dimethylpyrazo-1-ylmethyl) -2-chloroacetanilide

d.m-dimethyl-N- (1,3-dioxolan-2-ylimeethyl) -2-chloroacetanilide, d-dimethyl-N '(2-methoxyethyl) -28-chloroacetanilide,

2,6-dimethyl-N-isobutoxy-methyl-2-chloroacetanilide,

2,6-Didthyl-1'-methoxymethyl-2'-chloroacetic acid;

2,6-ethyl-Nt (n-butoxymethyl) -2-chloroacetate,

2,6-diethyl-N-methoxycarbonylmethyl-2-chloroacetanilide,

2,3,6-Trifluoromethyl-N- (1-pyrazol-ylmethyl) -2-chloroacetamide;

2,3-dimethylthisopropyl-2-chloroacetanilide,

2,6-diethyl-N- (2-nitropoxyethoxy) -2-chloroacetamide,

2- (2-Methyl-4-chlorophenoxy) -N-methoxyacetamide

2- (α-naphthoxy) -N, N-diethylpropionamide, .....

2,2-diphenyl-N, 1-dimethylacetyl amide,

N-benzyl-N-t-propyl-trimethyl-amide, α- (3,4,5-tribromo-6-pyrazol-1-yl) -N, N-dimethyl-propionamide,

N- (1,1-Dimethyl-propynyl) -3,5-dichloro-benzamide,

N-naphthalephthalamic acid,

Propionic acid 3,4-di-chloroanilide,

3.4- cyclopropanecarboxylic acid dichlorinililide,

Methacrylic acid 3,4-dichloroanilide;

3.4- (3-chlorophenyl) 2-methylpiperacarbonyl xylic acid,

N, 2,4-Dimethyl-5- (trifluoromethyl) sulfonylaminophenylacdaamide,

N4-methyl-5- (irifluoromethyl) sulfonylaminophenylacidide,

2-propicnylamino-4-methyl-5-chloro-azole,

2,6-Dimethyl-2,6-dimethylaminamide

O - (methylsulfonyl) glycolic acid,

N -isopropylene-3-O- (m-2-hydroxy-amino) glycolic acid,

N-tert-butan-3-ylanilino-O- (isopropylamino-sulfonyl) glycolic acid,

O- (m-dimethylaminophenylsulfonyl) glycolic acid,

2,6-dichloro-oblzamide,

2.6- Dichlorobenzoyl,

3,5-dibromo-4-hydroxybenzonitrile and its salts,

Oriilril and its salts,

3,5t-3-cm-4-hydroxy-2-2,4-dlnito-. fen-benzaldoxime and its salts,

3,5-dibromo-4-yroxy-5-nitro-4-nitrophen-1-benzaldoxime and its salts, sodium. pentachlorophenyl salt,

2,4t3ichlcrfdnylt4 ^< tnitrcfdnylt eaher

2,4,6tiricУlcrftnylt4‘-nitrcfdnylt e ^ er,

2-fluoro-4,6-dichlorophenyl-4-nitrophenyl ether,

2-chlorot4-t: ififlucrcrmdiylylylyl,,,,,,,,

2,4‘t3iniirct4-trifluoromethyl3ifdnylt elher,

2.4- 3-ld‘‘‘d melltltlt‘ mel mel mel mel mel mel mel,,,,,

2-chloro-N-trifluoromethylphenyl-3‘-ethoxy-4‘-nitrophenyl ether,

2-chloro (or-4-trifluoromethylphenyl-3'-carboxy-4'-nitrophenyl ether and its salts,

2-chloro-4-trifluoromethylphenyl-3‘-ethoxycarbonyl-4‘-nitrophenyl ether,

2-chloro-4-trifluoromethylphenyl-3 3- (2-fluoroethoxy) -4‘-nitro of enyl ether,

2-chloro-4-trifluoromethylphenyl-3‘-ethoxycarbonylmethylthio-4‘-nitrophenyl ether,

2-chloro-4-trifluoromethyl-3‘-methoxycarbonyl-4‘-nitrophenyl ether,

2,4,6-trichlorophenyl-3‘-ethoxycarbonylmethylthio-4‘-nitrophenyl ether,

2,3- dichloro-3 ^{<methoxycarbonyl-4} '

-nitrophenylether,,

2,4- dichlorophenyl F ^<-kaгboxy 4'-niarofenylether,

2- (3,4-dichlorophenyl) -4-methyl-1,2,2,4-oxadiazolidine-3,5-dione,

2- (3-tert-butoxycarbamoyloxyphenyl) -4-methyl-1,2,4,4-oxadiazolidine-3,4-dione,

2- (SOP ^ y ^ lkarbanioyloxyf phenyl) _-4-methyl-7 2,4-oxadiazolidine-3,5-dione;

2-phenyl-3-benzoxazin-4-one (4-broinfenyl) -3,4,5,9,10-pentazatetracyk 5,4,0,02-O4 ^'6 0 ⁸ '00] dodnka- 3,9-dinn,

2-ethoxy-2,3-dihydro-3,3-di-ethyl-5-benzofuranyl-inethanesulfonate,

2-ethoxy-2, f-dihydfo-3,3-dihydro-5-benzofuranyl dimethylaminosulfate,

2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranyl- (N-methyl-N-acetyl) aminosulfonate,

3,4-dichloro-1,2-benzoisothiazole,

--4-сЫог ^ пуИтИ allylsuccinic acid,

2-methyl-4,6-dinitrophenol and its salts and esters,

2-sec-butyl-4,6-dinitrophinol and its salts and esters,

2-sec-butyl-4,6-dinitrophenol acetate,

2-tert-butol-4,6-dimarophenol acetate,

2-tert-butyl-4,6-dinitrophenol and its salts,

2-tert-butyl-5-methyl-4,6-dimtrophenol and its salts,

2-tert-butyl-5-metho-4,6-dimtrophenoacetate,

2-sec.amo - 4,6-dinitrtifene- and its salts and esters,

O- (-α ·, α-dimethybenzyl) -3- (4-methylphenyl) urea,

O-tonyl-S- (2-m (thiocyclohexyl) urea, 1-phenyl-1-benzoyl-f, f-dimethylurea,

O- (4-chlorophenyl) -1-benzoyl-1,3-dimethylurea,

O- (4-chlorophenyl) -3,3-dimethylurea,

O- (4-chlorophenyl) -3- (ethoxy) -3- (O-butin-3-yl) urea,

O- (3,4-dichlorophenyl) -3,3-dinethylurea,

O- (3,4-dicollo-phenyl) -1-piperazin-1,3-dimethylurea,

O- (3,4-Difluoro-phenoxy) -3- (1,3-dimethyl-urea), 1- (4-isopropylphenyl) -3,3-dimethylurea,

O- [3-Trifluoromethylphenyl) -3,3-trimethylurea,

O- (3-ααβ / β-Etrafluoromethoxyphenyl) -3,3-dimethylurea

O- (f-tert-butylcarboyloxyphenyl) -3,3-dimethylurea,

O- (f-chloro-4-methylphenyl) -3,3-41 -pthylurea,

O- (3-chloro-4-methoxyphenyl) -3,3-dimethylurea,

3- (3 ^ -ШсЬки ’- ^ теиюхуОепуО) -3,3-

-dimethylnočovina,

O- (4- (4‘-chlorophenoxy) phenyl) -3,3-dimethylurea,

1- [4- (4‘-methoxyphenoxy) phenyl] -3,3-dimethylurea, 1-cyclooctyl-3,3-dimethylurea,

1- (hexahydro-4-methanindan-5-yl) -5-dimethylurea,

1- [1- or 2- (3a, 4,5,7,7a-hexahydro) -1,4,7-methanomdanyl] 1,3,3-dimethylurea,

1- (4-fluorophenyl) -1,3-carboxymethoxyl-3-methylurea, 1-thenyl-3-methyl-3-methoxy urea,

1- (4-chloro-phenyl) -3-methyl-3-methoxyl urea

1- (4-Bromo-phenyl) -1-methyl-6-methoxyl urea

1- (3,4-dichlorophenyl) -3-methyl-3-methoxyurea,

1- (е-Chloro-4-brpmЗeιnyl) --- Methyl 1-3-methoxyurea

1- (3-Chloro-4-isopropyl-phenyl) -3-methyl-3-methoxy-urea;

1- (3-chloro-4-methoxyphenyl) -3- (6-methyl-3-methoxyurea),

1- (3-tert-butylphenyl) 13-methyl-3-methyl-thiourea,

1- (2-benzthiazolyl) -1,3,3-dimethylurea,

1- (2-benzyl) -4-methylurea,

1- (5-difluoromethyl-1,3,4-? 8? 820? 1) -1,3-dimethylurea,

1- (4-benzyloxyphenyl) -3-methyl-ε-methanol urea, imidazolidiz-2-one-1-carboxylic acid isobutylamide,

1,2-Dimethyl-3,5-diphenylpyrazolium methylsulphate

1,2,4Чг1те1ЬуЬЗ, 5-У1Репу1ругагоИит-methylsulfate,

1,2-Dimethyl-4-bromo-3,5-diphenylpyrazolium methyl sulphate

1,3-dimethyl --- (3,4-dimethoxy-5-methyl) -5- (4-methylphenylsulfonyloxy) pyrazole, 1-acetyl-α-amino-4-methoxycarbonyl-5-methylpyrrole, ε-anan-14,4-tetrahydrocarbonyl51 -5 · methylpyrazole, ε-t-butyl: ω-amine 414-mercaptoxycarbonyl-5-methylpyrrole,

2, е, 5уtrichlorpеridin · 4lol

1-6-1- [3- (3-trifluoromethyl-phenyl) -pyrid-4-oz]

1-Methyl-4-phenylpyridine chloride,

1,1-Dimethylpyridrlium chloride, ε-phenynyl-1-hydroxy-6'-chloropyridazine, 1,1'-dimethyl-4,4'-dipyridyl · iumldil (methyl sulphate),

Ι, Γ-di- (ε, 5-dimethylmorpholinylmethyl) -4,4‘-diphidyloidium chloride, 1,1‘-ethylene-2,2‘-dipyridyliumidil bromide,

3- [11-N-thiocynyl-propylidene-6-ethyl-3,4-dihydro-2H-pyraz-2,4-dioD,

3- [1- (N-allylpyrimizo) propyl] -6-methyl-4, 4-dihydro-2H-pyrone-2,4-dione,

2- [1- (N-allyloxyimizo) propyl] -1,5,5-dimethylcyclphexane-1,1-dipnene and its salts,

2- (1- (N-allyloxy) butylbutyl) -5,5-dimethylmethylcyclophane-1,4-dione and its salts,

2- (1- (N-allylpentylamino) butylidene--5,5-dimethyl-4-methoxycarbonyl-cyclophenyl-1, ε-diPD and its salts,

2-ChloroZinc-2-acetic acid and its salts, esters and amides,

4-chlorophenoxyacetic acid and its salts, esters and amides,

2, C-dicЗtzpfxnoxpartic acid and its salts, esters and amides,

2,4,5-trichlorostezoxyacetic acid and its salts, esters and amides,

2-methyl-4-chlorophenoxyacetic acid and its salts, esters and amides,

SSG-trichloro-4-pyridinyloxyacetic acid and its salts, esters and amides, α-natoxyacetic acid methyl ester, 2- [4- (5'-bromopyridyl-2-oxy) phenoxy] propionic acid ethyl ester, 2- [4- (5 ') ethyl ester -iodo-pyridyl-2-oxy-phenoxy] -propionic acid, n-butyl ether-4- (4-oxo-pyridyl-4-oxy) -phenoxy] -propionic acid,

2- (2-methylphenoxy] propionic acid and its salts, esters and amides,

2- (4-chlorophenoxy) propionic acid and its salts, esters and amides,

........

2- (2,4-dichlorophenoxy) propionic acid and its salts, esters and amides,

2- (2,4,5-trichlorophenoxy) propionic acid and its salts, esters and amides,

2- (2-methyl-4-chlorophenoxy) propionic acid and its salts, esters and amides, 2- [4- (4‘-chlorophenoxymethyl) phenoxy] propionic acid methyl ester,

4- (2,4-dichlorophenoxy) butyric acid and its salts, esters and amides,

4- (2-methyl-4-chlorophenoxy) butyric acid and its salts, esters and amides, cyclohexyl 1-3- (2,4-dichlorophenoxy) acrylate,

9-hydroxyfluorene-9-carboxylic acid and its salts and esters,

2,3,6-trichlorophenylacetic acid and its salts and esters

4-chloro-2-oxobenzothiazolin-3-ylacetic acid and its salts and esters, gibeller acid and its salts, methylarsonic acid disodium salt, methylarsonic acid monosodium salt,

N-phosphonomethylglycine and its salts,

Ν, Ν-bis (phosphonomethyl Jglycine and its salts,

2-chloroethyl 2-chloroethanephosphonic acid ester, ammonium ethylcarbamoylphosphonate, di-n-butyl-1-n-butylamino-cyclohexylphosphonate, trithiobutylphosphite,

Ο, Ο-diisopropyl h5- (2-benzenesulfonylaminoethyl) phosphorodithionate,

2,3-dihydro-5,6-dimethyl-1,4-dithiine-1,1,4,4-tetraoxide,

5-tert-butyl-3- (2,4-dichloro-5-isopropoxyphenyl) -1,3,4-oxadiazol-2-one,

4,5-dichloro-2-trifluoromethylbenzimidazole and its salts, 1,2,3,6-tetrahydropyridazine-3,6-dione and its salts, mono-N-dimethyl succinic acid hydrazide and its salts, (2-chloroethyl) trimethylammonium chloride, (2-methyl-4-phenylsulfonyl) trifluoromethanesulfonanilide, 1,1-dimethyl-4,6-diisopropyl-5-indanylethylketone,

2- [1- (2,5-dimethylphenyl) ethylsulfonyl] pyridine-N-oxide,

2- (3'-trifluoromethylphenyl) -4H-3,1-benzoxazin-4-one,

2- (2-thienyl-4H-3,1-benzoxazin-4-one), sodium chlorate, ammonium rhodanide, calcium cyanamide,

2-chloro-4-trifluoromethyl-3'-ethoxycarbonyl-4'-nitrophenyl ether,

1- [4-benzyloxyphenyl) -3-methyl-3-methoxyurea,

2- [1- (2,5-dimethylphenyl) ethylsulfonyl] pyridine-N-oxide, 1-acetyl-3-anilino-4-methoxycarbonyl-5-methylpyrazole,

3-anilino-4-methoxycarbonyl-5-methylpyrazole,

3-tert-butylamino-4-methoxycarbonyl-5-methylpyrazole,

N-benzyl-N-isopropyltrimethylacetamide, 2- [4- (4'-chlorophenoxymethyl) phenoxy] propionic acid methyl ester, 2- [4- (5'-bromopyridyl-2-oxy) phenoxy] propionic acid ethyl ester, 2- [4- (5'-iodopyridyl-2-oxy) * phenoxy] propionic acid ethyl ester, 2- (4- (5'-iodopyridyl-2-oxy) phenoxy] propionic acid n-butyl ester,

2-chloro-4-trifluoromethylphenyl-3‘- (2-fluoroethoxy-4‘-nitrophenyl ether),

2-chloro-4-trifluoromethylphenyl-3- (ethoxycarbonyl) methylthio-4-nitrophenyl ether,

2,4,6-trichlorophenyl-3‘- (ethoxycarbonyl) methylthio-4-nitrophenyl ether,

2- [1- (N-ethoxyamino) butylidene] -5-

- (2-ethylthiopropyl) -3-hydroxycyclohex-2-en-1-one and its salts,

2- [1- (N-ethoxyamino) butylidene] -5-

- (2-phenylthiopropyl) -3-hydroxycyclohex-2-en-1-one and its salts, 4- [4- (4'-trifluoromethyl) phenoxy] pentene-2-carboxylic acid ethyl ester,

2-chloro-4-trifluoromethyl-3‘-methoxycarbonyl-4‘-nitrophenyl ether,

2,4-dichlorophenyl-3'-carboxy-4'-nitrophenyl ether and its salts,

4,5-dimethoxy-2- (3-a, N-trifluoro- (p-bromoethoxyphenyl) -3- [2H] -pyridazinone,

2,4-dichlorophenyl-3‘-ethoxyethoxyethoxy-4‘-nitrophenyl ether,

2,3-dihydro-3,3-dimethyl-5'-benzofuranyl ethanesulfonate,

N- [4-methoxy-6-methyl-1,3,5-triazin-2-ylaminocarbonyl] -2-chlorobenzenesulfonamide,

1- (3-chloro-4-thiophenyl) -3,3-dimethylurea, 2-methyl-4-chlorophenoxythioacetic acid ethyl ester,

2-chloro-3,5-diiodo-4-acetoxypyridine,

1,4- [2- (4-methylphenyl) ethoxy] phenyl-3-methyl-3-methoxyurea,

2,6-Dimethyl-N- (pyrazol-1-ylmethylenoxymethyl) -2-chloroacetanilide;

2-Methyl-6-ethyl-N- (pyrazol-1-ylmethylenoxymethyl) -2-chloroacetanilide

3- (O-methylcarbamoyl janilide 1- (-2 -2,4-dichlorophenoxyproponic acid),

3- (O-methylcarbamoyl) anilide-1-i (α-2-bromo-4-chlorophenoxypropionic acid),

2-methyl-6-ethyl-N- (pyrazol-1-yl-ethylenoxymethyl) -2-chloroacetanilide, methyl-N-dichlorofluoromethylsulfenyl-

- [3- (N‘-dichlorofluoromethylsulfenyl-N * -phenylcarbamoyloxy) phenyl] carbamate, methyl-N-dichlorofluoromethylsulfenyl- [3-

- (N‘-dichlorofluoromethylsulfenyl-N‘-3-methylphenylcarbamoyloxy) phenyl] carbamate,

N- (pyrazol-1-ylmethyl) -pyrazol-1-yl-acetic acid, 2,6-dimethyl-anilide;

N- (pyrazol-1-ylmethyl) -1,2,4-triazol-1-ylacetic acid 2,6-dimethylanilide,

2- (3‘-Trifluoromethylphenyl) -4H-3,1-benzoxazin-4-one,

2- (2-thienyl) -4H-3,1-benzoxazin-4-one.

In addition, it is useful to apply the compositions according to the invention, alone or in combination with other herbicides, also in admixture with other plant protection agents, for example with pesticides or with phytopathogenic fungi or bacteria. Further, it is of importance to be miscible with mineral salt solutions which are used to eliminate nutrient or trace element deficiencies.

Non-phytotoxic oils and oil concentrates may also be added.

Table 1

List of names of test plants abutilon (Abutilon theophrasti) Common oat (Avena sativa) Rape (Brassica napus)

227Q22 Blue Cornflower (Centaurea cyanus) Goosefoot (Chenopodium album) Durman (Datura stramonlum) Bedstraw (Galium aparine) Cotton (Gossypium hirsutum) Bladderwort (Ipomoea spp.) Dead-nettle (Laminum spp.)

Malva neglecta Rice (Oryza sativa) Mustard (Sinapis alba) Eggplant (Solanum nigrum) Wheat (Triticum aestivum) Speedwell (Veronica spp).

Table 2

Herbicidal activity of 5-auino-1-phenylpyrazole-4-carboxylic acid esters with pre-emergence application of 3.0 kg / ha of active substance (greenhouse experiment)

active substance number R1 R2 R3 6 CH3 Cl H 4 Cl Cl 6tC1 3 Cl Cl H 2 Cl Cl H 1 Cl Cl 6-C1 7. Br Br 6-Br

test plants and% damage

R4 Avena sativa Ipomoea spec. Sinapis alba —CH3 0 85 8Ό —CžH5 0 60 80 —CžH5 0 90 70 —CH3 - 70 100 ALIGN! —CH3 - 90 100 ALIGN! —CH3 20 May 100 ALIGN! 100 ALIGN!

Selective control of broadleaf weeds in cereals for post-emergence application in greenhouse

CO Гх m гЧ O я z ID ID ID ID O 4-> About θ 'θ' θ ' CM СЛ Св Ut е * S о it is that it X X X X in X he φ ф 5 & Й / Ч uouu ω lili 1 о S 1 sec r-4 »4 II II About CQ н <е CD X X CD я <С

Table 4

Herbicidal efficacy and greenhouse tolerance for some crop plants in posteme

effective test plants and percent damage

substance number kg / ha Brassica napus Gossypium sutumbir- Orzza sativa Chenopodium album Mavva neglecta Solanum nigrum 8 1.0 10 10 0 98 100 ALIGN! 80

Claims (2)

SUBJECT A herbicidal composition comprising a solid or liquid carrier and, as an active ingredient, at least one 5-amino-1-phenylpyrazole-4-carboxylic acid ester of the formula I according to the invention in which: R1 is methyl, chloro or bromo, R ² represents chlorine or bromine, R ³ represents hydrogen, chlorine or bromine, R 4 represents an alkyl group having 1 to 3 carbon atoms. 2. A composition according to claim 1, wherein the active ingredient is at least one compound selected from the group consisting of 5-amino-1- (2,4,6-tribromophenyl) pyrazole-4-carboxylic acid methyl ester, and 5-amino-1- (2,4,6-trb chlorophenyl) pyrazole-4-carboxylic acid methyl ester.