LT3371B - Method of cultured plants protection from phytotoxic herbicide effect - Google Patents

Description

The present invention relates to a method for protecting crop plants against phytotoxic effects of herbicides by employing protective agents comprising triazole compounds of formula (I):

in which

Z is the same or different substituents which may be halogen, nitro, cyano, trifluoromethyl, C ₁ . _4- alkyls, C 1-4 -alkoxyls, C 1-4 -alkylthio, where alkyl, alkoxyl and alkylthio may be substituted such as one or more halogen atoms, especially fluorine and chlorine; C ₃ . _6- cycloalkyls which may contain C 1-6 alkyl radicals; phenyl or phenoxyl residues which may be substituted such as one or more halogen atoms and / or one trifluoromethyl residue;

Y is hydrogen, C ₁ _ ₄ -alkyl, wherein the hydrogen may be partially or fully substituted with halogen and / or substituted with one substituent such as a C ^ alkoxy moiety or C ₁ _ ₄ -alkiltiogrupė; C ₂ _ ₆ alkenyl, C _{2nd 6-} alkynyl, C ₃ . _{A 6-} cycloalkyl residue which may contain C ₁ . _{A 4-} alkyl substituent and / or a dichlorvinyl residue;

Y is a hydroxyl group, a C ^ -alkyl radical, C ₃ _ ₆ cycloalkoxy moiety fenilaikoksilo moiety having 1-6 carbon atoms alkoxy moiety, phenoxy moiety, C ₂ _ ₆ -alkeniloksilo residue C _{2nd 6} -alkiniloksilo residue, C, _ ₆ -alkoxyl residue, C₁ galkiltiogrupė where the alkoxy moiety may be alkiltiogrupėje or C ₁ _ ₂ -alkoxyl substituted mono- and dialkylaminocarbonyl moiety having 1-4 carbon atoms in the alkyl moiety, phenylaminocarbonyl residue , An N-alkylphenylaminocarbonyl residue having 1-4 C atoms in the alkyl moiety, an alkylcarbonyloxyl residue having 1-6 C atoms in an alkyl moiety, C ₁ . _2- alkylthio, cyano or halogen; residue whose formula

or

wherein R is hydrogen or C ₁ _ ₄ alkyl, mono- dialkylamino having 1-4 C-atoms in the alkyl moiety, cikloalkilaminogrupė having

5-6 C-atoms in the cycloalkyl moiety, piperidine moiety, morpholine moiety or 2,6-dimethylmorpholine moiety;

a residue of the formula wherein R ¹ and R ² may be the same or different L 2 and are C ₄ -C ₄ alkyl radicals or R and R together may form a 5-, 6- or 7-membered ring; and n is an integer having the values 0, 1, or 3;

and, when X = OH, a salt of this compound which may be used in agriculture.

As salts, metal salts such as, for example, alkali or alkaline earth salts, in particular sodium or potassium salts, ammonium, mono-, di-, tri- or tetraalkylammonium-containing C 1-6 -alkyl radicals or mono- , di-, tri- or tetraalkanolammonium salts having 1-4 carbon atoms in alkanol moieties.

Most preferred are compounds of formula (I) wherein

Y is C ₁ . _{A 2-} alkyl radical whose hydrogens may be partially or completely substituted by fluorine, chlorine or bromine, Z are the same or different and are halogen atoms, C ₁ . _4- alkoxyl, C ₁ . _4- alkyl or trifluoromethyl, X is C 1-8 -alkoxyl or hydroxyl, on is 1, 2 or 3.

Particularly suitable among these compounds are those wherein

Y is a trifluoromethyl, dichloromethyl residue, CHF ₂ CF ₂ or methyl radical.

Unexpectedly, it has been found that said compounds of formula (I) can effectively reduce or completely eliminate the phytotoxic effects of plant protection products in crop plants. Similar compounds are called antidotes or Safener.

Some of the compounds of formula (I) are known from the scientific publications (Chem.Ber., 94, 1868 (1961), Chem. Ber., 96, 3210 (1963), Chem. Ber., 98, 642 (1965)) and from VFR patent no. 1123321. However, their effect as an antidote is not mentioned in these publications.

The compounds of formula (I) used in the present invention are novel and not described in the literature. These are the compounds of formula (I):

(I) in which

Z are the same or different and are halogen atoms, nitro groups, cyano groups, trifluoromethyl residues, C ₁ . _4- alkyl radicals, C ₁ -C ₄ -alkoxyl residues, C _x . ₄ alkylthio groups wherein alkyl, alkoxyl and alkylthio groups may be substituted such as one or more halogen atoms, especially fluorine and chlorine; C ₃ _ ₆ cycloalkyl residues which may be C _{x. 4-} alkyl radicals; phenyl and phenoxyl residues which may be substituted such as one or more halogen atoms and / or one trifluoromethyl residue;

Y is hydrogen, C ^ alkyl residue of the hydrogens may be partially or fully substituted with halogen and / or substituted with one substituent such as a C _l _ ₄ -alkoxyl or C ^ -alkiltiogrupę; C ₂ _ ₆ alkenyl moiety C ₂ _ ₆ alkynyl moiety C _{3rd 6} cycloalkyl residue, which can be C ₁ _ ₄ alkyl optionally substituted and / or dichlorovinyl moiety;

X is a hydroxyl group, a C ^ -alkyl radical, C ₃ _ ₆ cycloalkoxy moiety phenylalkoxy moiety having 1-6 carbon atoms alkoxy moiety, phenoxy moiety C _{2nd A 6-} alkenyloxyl residue, C ₂ . ₆ -alkiniloksilo residue, C ^ g alkoxy moieties of C ₁ _ ₆ -alkiltiogrupė where the alkoxy moiety, or C can be alkiltiogrupėje _{first 2-} alkoxyl substituents, mono and dialkylaminocarbonyl moiety having 1-4

Carbon atoms in the alkyl moiety, phenylaminocarbonyl residue N-alkilfenilaminokarbonilo moiety having 1-4 carbon atoms in the alkyl moiety, mono- or dialkylamino having 1-6 C-atoms in the alkyl moiety, C ₁ _ ₂ ~ alkylthio, cyano or halogen atom, ; a residue of formula or wherein R is hydrogen or C ₁ . _4- alkyl, mono or dialkylamino having 1-4 C atoms in the alkyl moiety, cycloalkylamino having

5-6 C-atoms in the alkyl moiety, piperidine residue, morpholine residue or 2,6-dimethylmorpholine residue; a residue of the formula wherein R ¹ and R ² may be the same or different and are C ₁ . _{The 4-} alkyl radicals or R ¹ and R ² together may form a 5-, 6- or 7-membered ring, when 0, 1, 2 or 3, or when X = OH, the salts of these compounds which may be used in agriculture in addition, when X = C ₁ _ ₄ alkyl, Y must be a trichloromethyl or dichloromethyl acid other than (I) the compounds of formula

a) Y is hydrogen, (Z) _n is hydrogen, chlorine at position 4, methyl group at position 4, methoxyl residue at position 2, methoxyl residue at position 4 or ethoxyl residue in the 4-position and X is a hydroxyl group, a methoxyl residue, or an ethoxyl residue,

b) Y is a methyl radical, (Z) _n is a nitro group at the 4 position, a methoxyl residue at the 4 position, a chlorine atom at the 2 position, a chlorine atom at the 4 position, a methoxyl residue at 2 and the nitro group at the 4 position or the methyl radical at the 2 position and the nitro group at the 4 position and X is a hydroxyl group or an ethoxyl residue, and

c) Y is an ethyl radical or CH (CH ₃ ) ₂ , (Z) _n is hydrogen and X is a methoxyl residue.

The compounds of the present invention are prepared by a process wherein (a) compounds of formula (II):

C 'o

II C-x '

NH _Z (II) wherein X 'is the same group as X except for the hydroxyl group is treated with ay compounds of formula Y-CO-C1 or a ₂ ) acid anhydride of formula Y-CO-O-CO- Y, or a ₃ ) an orthoether of formula YC (OR ¹ ) 3 wherein R ¹ is a C _1-4 alkyl radical, or

b) for compounds wherein Y = H, C ₁ _ ₄ alkyl, to obtain a compound of formula (III)

codr *

C OR ³

(III) wherein Y 'is hydrogen or C 1-6 alkyl and R ³ is

The C 1 -C 6 -alkoxyl or methyl is reacted with a base, in addition, the compounds of a _L and a ₂ , in some cases heated in acetic acid, and the compounds of formula (I) in some cases converted salts.

In the synthesis variants of α ₃ and α ₂ , in addition to the attachment of the chloro-anhydride or acid anhydride to the free amino group, a direct cyclization reaction occurs to give the compounds of formula (I). In addition, it was not unexpected that the a _x reaction occurs without the addition of a base. In contrast, the usual addition of a base promotes the formation of resinous products.

Formula (II) compounds interacting with a carboxylic acid chloride (YCOCJ, an acid anhydride or an ortoeteriu reaction expedient to carry out in an organic aprotic solvent. The acid anhydride, or ortoeterio case, (a ₂ or a ₃ variants) of the vehicle can play the appropriate reagent. Process for a Option ₃ is preferably carried out in the presence of an acidic catalyst, which may best be an organic acid such as para-toluene sulfuric acid.

Inert solvents used in variants a _x , a ₂ and a ₃ include aromatic compounds such as benzene, toluene, xylene, chlorobenzene, or cyclic compounds of the ether type such as tetrahydrofuran or dioxane or ketones such as acetone, as well as dipolar aprotic solvents such as dimethylformamide. Depending on the solvent used, the reaction temperature is from 10 ° C to the boiling point of the reaction mixture. If an aromatic solvent is used in variant a _x , a water separator is used to separate the water formed by the addition of the carbonic anhydride by boiling the reaction mixture. Variations of process a _x or a ₂ , depending on the remainder of the compounds (Z) _n and X of formula (II), initially give intermediates of formula (IV):

Y-C

II (IV) which can be distinguished, if necessary. If the reaction is carried out using the above solvent and is stopped at this stage, the further reaction must be carried out in acetic acid. For this purpose, the intermediate of formula (IV) is heated in acetic acid over a temperature range of about 50 ° C to the reflux temperature of the reaction mixture. This latter reaction may be carried out in the same vessel; before adding the acetic acid, the organic solvent used in the first step must be evaporated.

Variant b of method of preparation is in principle known from Chem. Ber., 96, 3120 (1963). Bases include, but are not limited to, inorganic bases, preferably sodium or potassium hydroxides. Compounds of formula (III) as described in this literature are prepared by reaction of the malonic acid acetamidoester or the acetoacetic acid acetaminoester compounds with a diazonium salt.

The compound of formula (I) obtained in the above manner can be converted into other compounds of formula (I) by conventional reactions. For example, a compound of formula (I) wherein X = OH can be obtained from an ester group of a compound of formula (I) by acidic or alkaline hydrolysis. Salts of this compound can be obtained from the compound of formula (I) having an acid group (X = OH) by addition of the appropriate base. Further, other esters or amides of formula (I) may be obtained from a compound of formula (I) having an ester group in conventional manner, for example by using the corresponding acid chloro anhydrides.

The preparation of compounds of formula (II) is in principle known. Compounds of formula (II) may be prepared by the action of achlorhydrazone of formula (V):

(Z)

NH-N *

(V) ammonia. On the other hand, the compounds of formula (V) may be obtained by reacting the phenyldiazonium salts with the haloacetoacetic acid esters or α-halo-β-dicetones. Both reactions are described in J. Chem. Soc., 87,

1895 (1905) and Ber. der dt. Chem. Ges., 50, 1482 (1917).

The compounds of formula (I) may, in particular, find application in the protection of crop plants against toxic side effects of herbicides.

The compounds of formula (I) may be used in combination with other herbicides, and may reduce or completely eliminate the adverse effects of the herbicides without reducing the activity of these herbicides in terms of harmful plants. Thanks to this, the scope of traditional plant protection products can be significantly extended.

The antidotes of phenoxyphenoxycarboxylic herbicides are the subject of European patent applications.

No. 31938. But these active.

Herbicides which can be reduced by the phytotoxic side effects of the compounds of formula (I) include, for example, carbamates, thiolcarbamates, haloacetanilides, substituted derivatives of phenoxy, naphthoxy and phenoxyphenoxycarboxylic acids such as quinolyloxy, quinoxalyloxy, pyridyloxy, esters of benzoxazolyloxy-, benzothiazolyloxyphenoxycarboxylic acids, as well as dimedonoxime derivatives.

Most preferred are esters of phenoxyphenoxy and heteroaryloxyphenoxycarboxylic acids. In addition, lower alkyl, alkenyl and alkynyl esters may be particularly used as esters.

Examples include, but are not limited to, the following herbicides:

u

A) herbicides fenoksifenoksi- heteroariloksifenoksikarboksilinių acids and C ₁ ^ ₄ alkyl, C ₂ _ ₄ alkenyl and C _{3rd 4-} alkynyl ester type, e.g.

2- / 4- (2,4-Dichlorophenoxy) -phenoxy / propionic acid methyl ester,

2- / 4- (4-Bromo-2-chlorophenoxy) -phenoxy / propionic acid methyl ester,

2- / 4- (4-Trifluoromethylphenoxy) -phenoxy / propionic acid methyl ester,

2- / 4- (2-Chloro-4-trifluoromethyl-phenoxy) -phenoxy / propionic acid methyl ester,

2- / 4- (2,4-Dichlorobenzyl) -phenoxy / propionic acid methyl ester,

Ethyl 4-, 4- (4-trifluoromethylphenoxy) -phenoxy / pent-2-enoic acid,

2- / 4- (3,5-Dichloropyridyl-2-oxy) -phenoxy / propionic acid ethyl ester,

Propargyl esters of 2- / 4- (3,5-dichloropyridyl-2-oxy) -phenoxy / propionic acid,

2- / 4- (6-Chloro-benzoxazol-2-yloxy) -phenoxy / propionic acid ethyl ester,

2- / 4- (6-Chloro-benzothiazol-2-yloxy) -phenoxy / propionic acid ethyl ester,

2- / 4- (3-Chloro-5-trifluoromethyl-2-pyridyloxy) -phenoxy / propionic acid methyl ester,

Butyl ester of 2- / 4- (5-trifluoromethyl-2-pyridyloxy) -phenoxy / propionic acid,

2- / 4- (6-Chloro-2-quinoxalyloxy) -phenoxy / propionic acid ethyl ester,

2- / 4- (6-Fluoro-2-quinoxalyloxy) -phenoxy / propionic acid ethyl ester,

2- / 4- (6-Chloro-2-quinolyloxy) -phenoxy / propionic acid ethyl ester;

B) chloroacetanilide herbicides, for example,

N-methoxymethyl-2,6-diethylchloroacetanilide,

N- (3'-methoxyprop-2'-ii) methyl-5-ethylchloroacetanilide, (3-methyl-1,2,4-oxydiazol-5-ylmethyl) chloroacetic acid

2,6-dimethylanilide;

C) thiocarbamates, for example,

S-ethyl-N, N-dipropargylthiocarbamate or S-ethyl-N, N-diisobutylthiocarbamate;

D) dimedone derivatives, for example,

2- (N-ethoxybutyrimidoyl) -5- (2-ethylthiopropyl) -3-oxy-2-cyclohexenone-1-as,

2- (N-ethoxybutyrimidoyl) -5- (2-phenylthiopropyl) -3-oxy-2-cyclohexenone-1-as; or

2- (1-Allyloxyiminobutyl) -4-methoxycarbonyl-5,5-dimethyl-3-oxocyclohexenol.

Quantitative antidote: Herbicide ratios can range from 1:10 to 10: 1, especially between 2: 1 and 1:10. In each case, the optimal amounts of antidote and herbicide will depend on the type of herbicide or antidote used and the type of plant being treated, and will be determined from time to time by appropriate tests.

The main applications of antidotes are primarily cereals (wheat, rye, barley, oats), rice, maize, Sorghum as well as cotton, sugar beet, cane and soybean.

Depending on their properties, the antidotes of formula (I) can be applied to the seeds of crop plants (seed dressing), either before sowing or in combination with herbicides before or after emergence of the plants. Pre-emergence tillage includes both pre-emergence tillage and pre-emergence tillage. It is best to use these antidotes in combination with herbicides. Mixtures made in certain containers or pre-assembled formations are used for this purpose.

The method of protecting crop plants from adverse phytotoxic effects of the herbicides according to the invention is characterized in that an effective amount of the compounds of formula (I) is used before, after or in combination with the use of the herbicide.

In addition, the compounds of formula (I) have fungicidal activity. Therefore, they can be used to control phytopathogenic fungi such as the black fungus, rust-causing fungus, Phytopthora, Betrytis, Pyrcularia Venturia inegualis. For purposes of use, the compounds of formula (I) may be formulated with dusting preparations, wettable powders, dispersions, emulsion concentrates, and the like together with the usual formulation aids. in the form in which they can be used as such or in solution or dispersed in a solvent (water) before use.

In addition, the compounds of formula (I) exhibit partial plant growth regulating activity. They are involved in plant-specific metabolism and can therefore be applied to influence the substances contained in the plant, as well as to facilitate harvesting, such as desiccation and plant growth enhancement.

According to the present invention, the material can be applied in the form of conventional preparations, for example, wettable powders, emulsifiable concentrates, spray solutions, dusts, stains, granules or micro-granulates.

Preparations, known as wettable powders, which are capable of dispersing uniformly in water, and which, in addition to the biologically active substance, contain, in addition to diluent or inert material, a wetting agent such as polyoxyethylated alkylphenol, fatty polyoxyethylated alcohol, alkyl or alkylphenylsulfonate; and a dispersant such as sodium salt of lignin sulphonic acid, sodium salt of 2,2'-dinaphthylmethane-6,6'-disulphuric acid, sodium salt of dibutylnaphthalic acid or oleylmethylurethic acid. Such a powder is obtained by conventional means, for example by grinding and mixing the components.

Emulsion concentrates may be prepared, for example, by dissolving the biologically active substance in an inert organic solvent such as butyl alcohol, cyclohexanone, dimethylformamide, xylene or a high boiling aromatic hydrocarbon EN 3371 B, or by adding one or more emulsifiers. If the biologically active substance is in liquid form, the use of the solvent may be totally or partially abandoned. Examples of emulsifiers include calcium salts of alkylarylsulphonic acids such as the calcium salt of dodecylbenzenesulphonic acids or nonionic emulsifiers such as esters of fatty acid polyglycols, polyaryl ethers of ethylene fatty alcohols, ethylene oxides of ethylene fatty acids, and fatty acid esters, sorbitan and fatty acid esters or sorbitan and polyoxyethylene ethers.

Dust preparations are obtained by grinding a biologically active substance with a finely divided solid such as talc, natural clays such as kaolin, bentonite, pyrophyllite or infusible earth.

Granular formulations are prepared either by spraying the biologically active agent onto a granular inert substance with adsorbent properties or by coating the carrier surface with a concentrate of the biologically active agent, using binders such as polyvinyl alcohol, polyacrylic acid sodium salt or mineral oil. The carrier material may be sand, kaolinite or granular inert material. Suitable biologically active substances may be granulated by conventional methods for preparing granular fertilizers; if necessary, granulation with fertilizers is possible.

The concentration of the biologically active substance in the wettable powder is about 10 to 90% by weight. The residue up to 100% by weight consists of the usual ingredients used in the preparation of the preparation. In the case of emulsion concentrates, the concentration of the biologically active substance may be from about 10 to 80% by weight. Dust formulations contain at least 5 to 20% by weight of the biologically active agent and about 1 to 1% by weight for the intended solutions. In the case of granular preparations, the amount of the biologically active substance depends in part on whether the active compound is in liquid or solid form, as well as on the excipient, excipient, etc. used for granulation.

material for spraying 20 weight

In addition, said biologically active agent formulations in some cases contain conventional adhesives, wetting agents, dispersants, emulsifiers, penetration enhancers, solvents, excipients, and carriers.

When using a commercially available formulation, the concentrate may in some cases be diluted in a conventional manner such as wettable powders, emulsifiable concentrates, dispersions, and micro-granulated formulations, with water. Dust and granular formulations and spray solutions are usually no longer diluted with other inert substances before use.

The required rate of application of the compounds of formula (I) used as antidotes, depending on the herbicide used, can vary within wide limits and in most cases is from 0.01 to 10 kg of biologically active substance per hectare.

The following examples further illustrate the present invention.

λ. Preparation examples

(a) The dust preparation was prepared by mixing 10 parts of a compound of formula (I) with 90 parts by weight of talc or inert material and grinding the mixture in a blow mill.

(b) A wettable powder which is readily dispersible in water, is obtained by mixing 25 parts by weight of a compound of formula (I), 64 parts by weight of quartz containing kaolin (inert substance), 10 parts by weight of potassium salt of lignin sulphonic acid and 1 part by weight humidifier and dispersant) and grinding the resulting mixture in a hot mill.

(c) The dispersible concentrate, which is readily dispersible in water, was prepared by mixing 20 parts by weight of a compound of formula (I), 6 parts by weight of alkylphenol polyglycol ether (Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 mol ethylene oxide) mineral oils (boiling point, e.g., about 255 > 377 ° C) and blending the resulting mixture in a ball mill until the particle size is less than 5 microns.

d) The emulsion concentrate was prepared from 15 parts by weight of the compound of formula (I), 75 parts by weight of cyclohexanone (solvent) and 10 parts by weight of oxyethylated nonylphenol (emulsifier).

(e) The concentrate, which readily emulsifies in water, consisting of the phenoxycarboxylic acid ester and the antidote (10: 1) was prepared from:

18th 12% by weight 2- / 4- (6-Chloro-benzoxazol-2-yloxy) -phenoxy / -propionic acid ethyl ester, 1.20% by weight A compound of formula (I),

69.00% by weight of xylene,

7.80% by weight dodecylbenzene sulfuric acid calcium salt, 6.00% by weight of ethoxylated nonylphenol (10 mol ethylene oxide), 4.00% by weight of ethoxylated castor oil (40 mol ethylene oxide).

The preparation was prepared as described in Example a).

(f) The concentrate, which readily emulsifies in water, consisting of the phenoxycarbonic acid ester and the antidote (1:10), has been prepared from:

4.0% by weight 2- / 4- (6-chlorobenzoxazol-2-yloxy) phenoxy / propionic acid ethyl ester, 40.0% by weight A compound of formula (I), 30.0% by weight xylene, 20.0% by weight cyclohexanone, 4.0% by weight calcium salts of dodecylbenzene sulphonic acid, 2.0% by weight of ethoxylated castor oil (40 mol ethylene oxide).

B. Chemical Examples

Intermediates

1. g-Chloro-α- (3-trifluoromethylphenylhydrazone) -glyoxylic acid methyl ester

161.1 g (1.0 mol) of 3-trifluoromethylaniline are dissolved in a mixture of 400 ml of water and 326 ml of concentrated hydrochloric acid and 70 g of sodium nitrite solution in 400 ml of water are added dropwise at 0 ° C.

The resulting diazonium salt solution is cooled vigorously immediately after dropwise addition and added dropwise, under vigorous stirring, to a cooled solution of 165.5 g of gchloroacetoacetic acid methyl ester, 800 ml of water, 444 g of sodium acetate and 100 ml of ethyl alcohol with vigorous stirring. After stirring for a further 3 hours, the reaction mixture was diluted with water, the product was filtered off and the crude product was boiled in methyl alcohol.

Yield: 263.6 g (94%); melt mp: 145 ° C.

. g-Amino-g- (3-trifluoromethylphenylhydrazone) -glyoxylic acid methyl ester

Dissolve 100 g (0.356 mol) of methyl g-chloro-g- (3-trifluoromethylphenylhydrazone) -glyoxylic acid methyl ester in 560 ml of tetrahydrofuran and add 61 g of 25% aqueous ammonia at 15-20 ° C. The mixture was then stirred at room temperature for 5 hours and poured into water. The product is filtered off and boiled in methyl alcohol.

Yield: 88.3 g (95%); melt

138 ° C.

Finished products

3. 1- (3-Trifluoromethylphenyl) -3-methoxycarbonyl-5-trichloromethyl-1,2,4-triazole

(a) solvent used in toluene

25.1 g (0.1 mol) of a-amino-α- (3-trifluoromethylphenylhydrazone) -glyoxylic acid methyl ester are added to 150 ml of toluene and stirred under stirring.

0.12 mol of trichloroacetyl chloride. Immediately, the drip reaction mixture is boiled dropwise under reflux and a water separator; boil until water stops (about 1 hour).

The reaction mixture was cooled, the toluene solution was washed with water and the toluene evaporated in vacuo. The resulting crude product precipitate is recrystallized from methyl alcohol.

Yield: 24 g (61.7%). The crystalline substance is slightly yellowish, m.p. mp: 92-93 ° C.

(b) Tetrahydrofuran as the solvent

Dissolve 182.8 g (0.7 mol) of a-amino-α- (3-trifluoromethylphenylhydrazone) -glyoxylic acid methyl ester in 1200 ml of tetrahydrofuran and add 191 g (1.05 mol) in 10 ml without stirring and stirring. ) trichloroacetyl chloride. The reaction mixture was stirred at room temperature for 30 minutes, then refluxed for 15 minutes, then stirred at room temperature for a further 5 hours. The mixture is poured into water, the precipitated crystalline precipitate is filtered off and washed with water. The crystalline material is yellowish in color.

Yield: 233.3 g (85%); melt mp: 90 ° C.

After recrystallization from methyl alcohol, the material has a melting point of 92-93 ° C.

4. 1- (3-Trifluoromethylphenyl) -5-trichloromethyl-1,2,4-triazole-carboxylic acid

1- (3-Trifluoromethylphenyl) -3-methoxycarbonyl-5-trichloromethyl-1,2,4-triazole (210 g, 0.54 mol) is added to 540 ml of methyl alcohol and mixed with 0.57 mol of sodium hydroxide (22 ml). , 8 g) in 100 ml of water. After stirring for 5 hours at room temperature, the mixture is poured into 4000 ml of water, the insoluble material is filtered off and the clear filtrate is acidified to pH = 1 with hydrochloric acid. The precipitated colorless crystalline material is filtered off and washed with water. The water-insoluble residue, the carboxylic acid sodium salt, is dissolved in a mixture of 2000 ml of methanol and 1000 ml of water, the solution is acidified to pH = 1 with hydrochloric acid, and the crystalline colorless precipitate is filtered off and washed with water. The two carboxylic acid fractions are mixed and recrystallized from 1000 ml of toluene.

Yield: 174 g (84%); melt mp: 133-136 ° C.

. 1- (3-Trifluoromethylphenyl) -3-isopropoxycarbonyl-5-trichloromethyl-1,2,4-triazole g (0.0534 mol) 1- (3-Trifluoromethylphenyl) -5-trichloromethyl-1,2,4-triazolecarboxylic acid and 70 ml of thionyl chloride are refluxed for 30 minutes, thionyl chloride is vacuum dried, followed by crude chloro anhydride and 120 ml is refluxed for 60 minutes. After refluxing the excess carboxylic acid isopropyl alcohol solution is cooled, poured into a water / ice mixture and the precipitated crystalline product is filtered off.

The crude colorless crystalline product was stirred at room temperature in a mixture of methanol: water 1: 2 (50 mL), filtered again and air dried.

Yield: 19.4 g (87.3%); melt mp: 91 ° C.

6. 1- (3-Trifluoromethylphenyl) -5-trichloromethyl-1,2,4-triazole-carboxylic acid 3-trifluoromethylanilide

0.0345 mol of the carboxylic acid is converted into its chloro anhydride according to the procedure described in Example 5, which is dissolved in 80 ml of toluene. The resulting solution was treated with 0.0345 moles (5.56 g) and 0.0345 moles at room temperature for 20 minutes. After stirring for 5 hours at room temperature, the toluene was recrystallized from a dropwise addition of 3-trifluoromethylaniline triethylamine (3.5). g), the solution is evaporated in vacuo and 40 ml of methyl alcohol at room temperature.

Colorless crystals were obtained, m.p. temp. 126 ° C.

Yield: 14.4 g (81%).

7. 1- (3-Trifluoromethylphenyl) -3-methoxycarbonyl-5-dichloromethyl-1,2,4-triazole

Dissolve 0.1 mol (26.1 g) of α-amino-α- (3-trifluoromethylphenylhydrazone) -glyoxylic acid methyl ester in 150 ml of toluene and add this solution to 0.105 mil (15.5 g) of dichloroacetyl chloride at room temperature with stirring. The reaction mixture is then refluxed for 60 minutes with a water separator. The reaction mixture was cooled, washed several times with water and the toluene evaporated in vacuo. A light honey-colored syrupy residue is obtained.

Yield: 28.2 g (80%); n _D ³⁰ = 1.5259.

NMR Spectrum (CDCl ₃ ): COOCH ₃ δ 4.05; CHCl ₂ δ 6.72;

R _f = 0.52 (2: 1 mixture of toluene and ethyl acetate).

8. 1- (2,6-Diethylphenyl) -3-methoxycarbonyl-5-trichloromethyl-1,2,4-triazole

0.15 mol (37.4 g) of α-amino-α- (2,6-diethylphenylhydrazone) -glyoxylic acid methyl ester is dissolved in 155 ml of tetrahydrofuran and the resulting solution is mixed with 0.194 mol (35.4 g) of trichloroacetyl chloride. The mixture is stirred for 3 hours at room temperature, the reaction mixture is poured into water, extracted with methylene chloride, the organic layer is washed with water and the solvent is evaporated off under vacuum.

Yield: 51.7 g (91.5%).

The resulting light brown syrup is an open-chain compound based on NMR spectrum and elemental analysis.

n

18.9 g (0.047 mol) of this compound are dissolved in 120 ml of glacial acetic acid and refluxed.

1.5 hours. The reaction mixture was cooled, poured into water and extracted with methylene chloride. The organic layer was washed three times with water and the solvent was evaporated in vacuo.

The remaining yellowish crystalline material is mixed with 20 ml of methyl alcohol and then filtered.

Yield: 16.4 g (91%); melt mp: 76-77 ° C.

9. 1- (3-Trifluoromethylphenyl) -3-methoxycarbonyl-5- (2,2-dimethyl-ethen-1-yl) -1,2,4-triazole

Dissolve 26.1 g (0.1 mol) of a-amino-α- (3-trifluoromethylphenylhydrazone) -glyoxylic acid methyl ester in 150 ml of tetrahydrofuran and add 15.4 g (0.13 mol) of β in this solution without freezing over 10 minutes, β-dimethylacrylic acid chloro anhydride. The reaction mixture is refluxed for 1 hour, most of the tetrahydrofuran is distilled off at atmospheric pressure, and the remaining reaction mixture is mixed with water. The product is decanted and recrystallized from methyl alcohol.

Yield: 24 g (73.7%); melt mp: 143-144 ° C.

10. 1- (4-Fluorophenyl) -3-methoxycarbonyl-5-methoxymethyl-1,2,4-triazole

21.1 g (0.1 mol) of methyl α-amino-α- (4-fluorophenylhydrazone) glyoxylic acid are dissolved in 140 ml of toluene and 14.1 g (0.13 mol) of methoxyacetyl chloride are added dropwise over 10 minutes without refrigeration. . The reaction mixture was refluxed for 1.5 hours, cooled, the toluene solution was washed twice with water (200 mL each), the toluene evaporated in vacuo and the resulting residue was recrystallized from methyl alcohol.

Yield: 15.2 g (57.4%); melt mp: 93-94 ° C.

11. 1- (2,4-Dichlorophenyl) -3-ethoxycarbonyl-5-methyl-1,2,4-triazole IIa) α- (2,4-Dichlorophenyl azo) -acetaminomalonic acid diethyl ester

Briefly boil 0.2 mol (33.4 g) of 2,4-dichloroaniline in 60 ml water and 75 ml concentrated hydrochloric acid, cool the suspension to + 5 ° C and diazotize at this temperature by adding 0.2 mol (13.7 g). (g) sodium nitrite in 25 ml water.

The diazone salt solution is added dropwise at 5-7 ° C over 15 minutes to a vigorously stirred mixture of 300 ml of ethyl alcohol, 200 ml of water, 100 g of sodium acetate and 0.2 mol (43.3 g) of acetaminomalonic acid diethyl ester. The mixture was stirred at room temperature for an additional 1 hour, poured into water, the crystalline material precipitated, filtered off and washed with water. After recrystallization from a mixture of ethyl alcohol and water, the crystalline material has a melting point of 123-124 ° C.

Yield: 71 g (91%).

11b) 1- (2,4-Dichlorophenyl) -5-methyl-1,2,4-triazolecarboxylic acid g (0.1 mol) of the product obtained in Example 11a, 165 ml of water and 24.2 g of potassium hydroxide are refluxed. the clear solution is cooled to 60 ° C under reflux for 5 minutes, acidified with concentrated hydrochloric acid, and the precipitated 1- (2,4-dichlorophenyl) -5-methyl-1,2,4-triazolecarboxylic acid is filtered off and washed with water, until it becomes neutral.

Yield: 25.6 g (94%); melt mp: 163-164 ° C.

11c) 1- (2,4-Dichlorophenyl) -3-ethoxycarbonyl-5-methyl-1,2,4-triazole

0.10 mol of the product of Example 11b and 150 ml of thionyl chloride are refluxed for 2 hours, the excess thionyl chloride is removed in vacuo to give crude chloro anhydride and 500 ml of ethyl alcohol is refluxed for 30 minutes. The reaction mixture is poured into water, the precipitated crystalline material is filtered off and washed with water until it becomes neutral.

Yield: 24 g (80%); melt mp: 131-132 ° C.

After recrystallization from methyl alcohol, the crystalline product has a melting point of 133-134 ° C.

12. 1- (2,4-Dichlorophenyl) -3-ethoxycarbonyl-5-methyl-1,2,4-triazole

12a) 0.1 mol (27.6 g) of ethyl ester of? -Amino-α- (2,4-dichlorophenylhydrazone) -glyoxylic acid and 150 ml of acetic anhydride are refluxed for 2 hours, the excess acetic anhydride is evaporated off under vacuum and the remaining crude product is recrystallized from ethyl alcohol.

Yield: 21.6 g (72%); melt mp: 133-134 ° C.

12b) 0.1 mole (27.5 g) of ethyl α-amino-α- (2,4-dichlorophenylhydrazone) -glyoxylic acid and 130 ml of triethyl orthoether are refluxed for 4 hours, the excess orthoether is evaporated in vacuo and the residue is evaporated. recrystallization from ethyl alcohol.

Yield: 18.9 g (63%); melt mp: 133-134 ° C.

13. 1- (2,4-Dichlorophenyl) -3-ethoxycarbonyl-1,2,4-triazole

0.1 mol (27.6 g) of α-amino-α- (2,4-dichlorophenylhydrazone) -glyoxylic acid diethyl ester and 120 ml of formic acid trimethylorthoether are refluxed for 5 hours, the excess orthoether is evaporated in vacuo and the residue is recrystallized from ethyl of alcohol.

Yield: 21.4 g (75%); melt mp: 105-106 ° C.

14. 1-Phenyl-3-acetyl-5-trichloromethyl-1,2,4-triazole

0.1 mol (17.7 g) of α-amino-phenyl-hydrazonomethylglyoxal in 150 ml of tetrahydrofuran is stirred with 0.13 mol (23.6 g) of trichloroacetyl chloride. The reaction mixture is stirred and refluxed for 1 hour, poured into 1 L of water, the precipitate is decanted and the product is recrystallized from methyl alcohol.

Yield: 20.1 g (66%); melt m.p. 139-140 ° C.

Following the procedures described in Examples 3-14, the compounds of formula (I) shown in Table ΙΒ are obtained.

Table 1B

For example, No. (Z) _n Y X Lt (° C) 30 ⁿ D Received according to For example, No. 1 2 3 4 5 6th 15th 3-chloro- CC1 ₃ - ethoxy 76-77 3a 16th 3-chloro- CC1 ₃ - OH 124-127 4 17th 3-chloro- CHC1 ₂ - ethoxy syrup figure material 3a 18th 2-chloro- CC1 ₃ - ethoxy 99-100 3a 19th 2-chloro- CC1 ₃ - OH 204-205 4 20th 2-chloro- CC1 ₃ - non-toxic 114-115 3b 21st 2-chloro- CC13- h-propoxy 90-92 5 22nd 4-chloro- CHC1 ₂ - methoxy 152-153 3a 23rd 3,5-dichloro- chci ₂ - methoxy 1,5809 3a 24th 4-nitro chci ₂ - methoxy 149-150 3a 25th 3,5-dichloro- CC1 ₃ - methoxy 143-145 3b 26th 3,5-dichloro- CC1 ₃ - OH 194-195 4 27th 2-chloro- CHC1 ₂ - ethoxy 135-136 3a 28th 3-chloro- chci ₂ - OH 114 4 29th 2-chloro- chci ₂ - methoxy 158 3a 30th 4-nitro CC1 ₃ - methoxy 201-203 3b 31st H CC1 ₃ - methoxy 103-104 3b 32 H CC1 ₃ - OH 154-156 4 33 4-fluoro CHC1 ₂ - methoxy 168 3a

Continuation of Table 1B

1 2 3 4 5 6th 34 3-cyano- CC1 ₃ - OH 155 4 35 4-chloro- phenoxy CC1 ₃ - OH 142 4 36 2,4-dichloro CC1 ₃ - ethoxy 111-112 8th 37 2,4-dichloro CC1 ₃ - OH 156 4 38 4-chloro- phenoxy CC1 ₃ - methoxy 1.5925 3b 39 2,4-dichloro CHC1 ₂ - methoxy 147 3a 40 2-chloro- chci ₂ - OH 188-189 4 41 2,4-dichloro CC1 ₃ - methoxy syrup in the form of wood 3b 42 2,4-dichlorophenoxy CC1 ₃ - OH 141 4 43 2,4-dichloro CC1 ₃ - -NHCgH ₅ 215-217 6th 44 2,4-dichloro CC1 ₃ - -NBDgHrS-CFis 166-167 6th 45 3,5-dichloro- CC1 ₃ - -NHC-3-CF ₃ 160-161 6th 46th 2,4-dichloro-5-methoxy CC1 ₃ - 173 6th 47 2,4-dichloro CC1 ₃ - methoxy 162-163 3b 48 2,4-dichloro CC1 ₃ - n-butoxy 66-67 5 49 2-methyl CC1 ₃ - -NH-O 166 6th 50 2-methyl 4-chloro- CC1 ₃ - -NH- ^ OCHf 167-168 6th

Continuation of Table 1B

1 2 3 4 5 6th 51 52 2,4-dichloro-3-CF ₃ CCI3- CC1 ₃ - -OCHoC-N-CIL · 2 n » ^J 0 c ₆ H ₅ ethoxy- 187-188 64 5x 3a 53 3,5-dichloro- CC1 ₃ - -OO-C-N-O-II 1 OC ₆ H ₅ 203 6th 54 2-methyl 4-chloro- ccia- CL 203 6th 55 2,4-dichloro CC13- 193-194 6th 56 2,4-dichloro CC1 ₃ - "'Ve % 68-72 6th 57 2,4-dichloro CC1 ₃ - 205-207 6th 58 4-chloro- CC1 ₃ - methoxy 136-137 3b 59 4-chloro- 3-chloro- CC1 ₃ - -OH 145-147 4 60 3-chloro- 4-fluoro CC1 ₃ - - ° XE> 131-132 5 61 3-chloro- 4-fluoro cci ₃ - -OO-CH (CH ₃ ) ₂ 122-123 5 62 2,4-dichloro CC1 ₃ - - / «- Ο 160-163 6th 63 2,4-dichloro CC13- -NfCAh glass hunts 6th 64 4-methyl CC1 ₃ - -OH 146 4

Continuation of Table 1B

1 2 3 4 5 6th 65 4-methyl CC1 ₃ - methoxy 132-134 3b 66 4-fluoro CC1 ₃ - methoxy 113-114 3b 67 2-methyl 4-chloro- CC1 ₃ - methoxy 117-118 8th 68 2-methyl 4-chloro- CC1 ₃ - methoxy 125-126 3b 69 3-cyano- CC1 ₃ - methoxy 125-126 3b 70 2,4-dichloro CC1 ₃ - -OCH (CH ₃ ) ₂ 154-155 5 71 2,4-dichloro CC1 ₃ - n-prcpoxy- 129-130 5 72 4-fluoro CC1 ₃ - -OH 131-132 4 73 4-fluoro CC1 ₃ - n-prcpoxy- 120-121 5 74 3-chloro- 4-fluoro CC1 ₃ - methoxy 114-115 3b 75 2,6-diethyl- CC1 ₃ - -OH 193-195 4 76 2,4-dichloro CC1 ₃ - -OCH ₂ CH (CH ₃ ) ₂ 119-121 5 77 2-chloro- CC1 ₃ - -OCH (CH ₃ ) ₂ 131-132 5 78 2,4-dichloro CC1 ₃ - methoxy 155 3b 79 2,4-dichloro CC1 ₃ - -OH 215 4 80 2-methyl 4-chloro- CC1 ₃ - -OH 112 4 81 2-chloro- CC1 ₃ - -OCH ₂ CH (CH ₃ ) ₂ 79-80 5 82 2-methyl 4-chloro- CC1 ₃ - -OCIįC-N-CeĘ II 1 och ₃ 153 5x

Continuation of Table 1B

1 2 3 4 5 6th 83 3-chloro- 4-fluoro CC1 ₃ - ethoxy 118-119 8th 84 3-chloro- 4-fluoro CC1 ₃ - -OH 174 4 85 4-fluoro CC1 ₃ - -OCH ₂ CH (CH ₃ ) ₂ 103-104 5 86 2-methyl 4-chloro- CC1 ₃ - n-butoxy 112 5 87 4-chloro- CC1 ₃ - ethoxy 161-162 8th 88 4-methyl- CC1 ₃ - -OCH (CH ₃ ) ₂ 154-155 5 89 H CC1 ₂ - -OH 185 4 90 2,4-dichloro CF ₃ - methoxy 131 3b 91 4-methyl CC1 ₃ - ethoxy 104-105 8th 92 4-methyl cci ₃ - -OCH ₂ CH (CH ₃ ) ₂ 125-126 5 93 2,4-Di chlorine phenoxy CC1 ₃ - ethoxy 147 8th 94 2,4-Di chlorine phenoxy CC1 ₃ - n-propoxy 99 5 95 4-fluoro CF ₃ - methoxy 87-88 3b 96 4-chloro- CC1 ₃ - -OCH ₂ CH (CH ₃ ) ₂ 138-139 5 97 2,6-diethyl- CC1 ₃ - ethoxy 96-97 8th 98 3,4-dichloro CC1 ₃ - methoxy 133 3b 99 2,6-diethyl- CC1 ₃ - -One 233-234 4 100 2,6-diethyl- CC1 ₃ - n-propoxy 1.5390 5

Continuation of Table 1B

1 2 3 4 5 6th 101 2,6-diethyl- CC1 ₃ - -OCH (CH ₃ ) ₂ 83-84 5 102 2,6-diethyl- CC1 ₃ - -OCH (CH ₃ ) 2 1,5147 5 103 3,4-dichloro CC1 ₃ - -OH 167-168 4 104 2-CF ₃ , 4-chloro- CC1 ₃ - methoxy 110 3a 105 2-CF ₃ , 4chloro- CC1 ₃ - -OH 143-145 4 106 2-F, 4-C1, 5-methoxy CC1 ₃ - methoxy 177-178 3a 107 2-F, 4-Cl, 5-methoxy CC1 ₃ - -OH 176 4 108 2-CHF ₂ CFįO- CC13- methoxy 116-117 3a 109 3-αηκτρ- cci ₃ - methoxy syrup figure hunts 3a 110 2-methyl 3-chloro- CC1 ₃ - methoxy 144-145 3a 111 2,6-dichloro- CC1 ₃ - methoxy 143-144 3a 112 2.5-Dim Toxic-4- chlorine CC1 ₃ - methoxy 149 3a 113 2.5-Dim Toxic-4- chlorine CC1 ₃ OH- 223-224 4 114 3,5-Di chloro-4- methoxy CC1 ₃ - methoxy 148-149 3a 115 3,5-Di chloro-4- methoxy cci ₃ - -OH 150 4

Continuation of Table 1B

1 2 3 4 5 6th 116 2-chloro- 4-bromo CC1 ₃ - ethoxy 113-114 3a 117 2-chloro-4- bromine CC1 ₃ - -OH 220 4 118 2-bromo CC1 ₃ - methoxy 126-127 3a 119 2-bromo CC1 ₃ - -OH 195-196 4 120 2,4-dichloro CC1 ₃ - -OCH ₂ CH ₂ Cl 88-89 5 121 3-CHClKFp- CC1 ₃ - -OH 126-130 4 122 2-methyl 4-chloro- CC1 ₃ - -CH ₃ 141 14th 123 3-methyl-4-CHF ₂ CF CFO- CC1 ₃ - -ch ₃ 119-120 14th 124 2,4-dichloro CC1 ₃ - -ch ₃ 120-121 14th 125 3-CFjO- CC1 ₃ - —CH ₃ 92-93 14th 126 3-CHCl ₂ CFp- CC1 ₃ - -ch ₃ 114-115 14th 127 H ccl ₃ - -ch ₃ 139-140 14th 128 2-chloro- CC1 ₃ - -ch ₃ 121-122 14th 129 3-CClF ₂ CC1 ₃ - -ch ₃ in the form of syrup. hunts 14th 130 4-chloro- (CH ₃ ) ₂ c = ch- methoxy 118-119 9th 131 2-methyl 4-chloro- (CH ₃ ) ₂ C = CH- methoxy 142-143 9th 132 2-chloro- ch ₂ ci- methoxy 112-113 10th 133 2-methyl 4-chloro- ch ₃ - methoxy 73 10th

Continuation of Table IB

1 2 3 4 5 134 3-chloro- 4-fluoro (CH ₃ ) ₂ c = ch- methoxy 185-186 135 2,4-Dichloro-5-methoxy- (CH ₃ ) ₂ C = CH- methoxy 200-201 136 3,4-dichloro chci ₂ -cf ₂ - ethoxy 1,5458 137 2-methyl 4-chloro- chci ₂ -cf ₂ - ethoxy 1.5272 138 2-methyl 4-chloro- chf ₂ -chf ₂ - ethoxy 1,4991 139 4-fluoro chf ₂ -cf ₂ - methoxy 66-67 140 2-chloro- (CH ₃ ) ₂ C = CH + -OH 194 141 3,4-dichloro cf ₂ h-cf ₂ - ethoxy 1,5198 142 2,4-Di chloro-5- methoxy CF2H-CF ₂ - methoxy 112-113 143 2-methyl 4-chloro- ch ₃ ch = ch- methoxy 175-176 144 CL 4-fluoro Ct = CH- ^ ch ₃ ch ₃ methoxy 149-150 145 3-CF ₃ chf ₂ -cf ₂ - methoxy syrup fig. 146 2,4-dichloro chf ₂ -cf ₂ - ethoxy VI 147 2,4-dichloro chf ₂ - (CF ₂ ) ₃ - ethoxy 115-116 148 2,4-dichloro CBrF ₂ -CF ₂ - ethoxy 100-101 149 2,4-dichloro chf ₂ -cf ₂ - -OH 123-124 150 2-chloro- ch ₃ - -OH 190

Continuation of Table 1B

1 2 3 4 5 6th 151 2-chloro- ch ₃ ethoxy 110-111 11c 152 4-chloro- ch ₃ - -OH 172 11b 153 4-chloro- ch ₃ - ethoxy 115 11c 154 3-chloro- 4-fluoro ch ₃ - -OH 183 11b 155 4-fluoro ch ₃ - -OH 177 11b 156 2-methyl 4-chloro- ch ₃ - -OH 177-178 11b 157 2,4-Di chloro-5- methoxy ch ₃ - -OH 193-195 11b 158 2,4-dichloro ch ₃ - methoxy 180-181 11c 159 3-chloro- 4-fluoro ch ₃ - methoxy 140-142 11c 160 3-chloro- 4-fluoro ch ₃ - ethoxy 114-115 11c 161 2,6-diethyl- chf ₂ -cf ₂ - -OH 222-223 4 162 4-fluoro ch ₃ - ethoxy 105-106 11c 163 2-methyl 4-chloro- ch ₃ - ethoxy 153-154 11c 164 2,4-dichloro H- -OH 185-186 4 165 2,4-dichloro H- ethoxy 105-106 13th 166 4-methyl ch ₃ - ethoxy 1.5466 11c 167 4-methyl ch ₃ - -OH 183 11b

Continuation of Table 1B

12 3 4 5 6th 168 2-Chloro-CH ₃ - 4-Bromo- ethoxy 142-143 11c 169 2-chloro-CH ₃ - 4-bromo -OH 172-173 11b 170 3-CF ₃ CH ₃ - -OH 164-165 11b 171 2,4-Dichloro-CH ₃ - ethoxy 133-134 11c 172 2,4-Dichloro-CH ₃ - -OH 163-164 11b The reaction is performed toluene with equimolarly alcohol content and triethylamine , how of acid acceptors. C. Biological samples Example 1 Wheat was grown in the orangery 9 cm diameter in cups up to 3-4 leaf stage, then they were treated with a herbicide and relevant in this in the invention with the compound described. Herbicides and in this in the invention the formulas (I) are described compounds was used aqueous suspensions or emulsions in the form of;

conversion rate 800 l / ha. After 3 weeks post-treatment, the type of damage caused by the herbicide was evaluated and the degree of sustained growth inhibition was considered.

The results presented in Table 1 clearly show that the compounds of the present invention are very effective in reducing the severe damage caused by the action of the herbicide.

Even with a large overdose of herbicide H (2.0 kg active ingredient / ha), the symptoms of the damage caused by the herbicide are greatly reduced and only minor damage remains. Thus, these compounds have good activity as antidotes. It is understood that minor damage is completely eliminated (see example 2). Thus, mixtures of the herbicides and the corresponding compounds of the present invention can be used in the selective control of weeds growing among cereal kernels.

table

H Compounds For example, No. The dose a.m. kg / ha Herbicidal activity, %, TA 1 2 3 4 H - 2.0 75 H + 17th 2.0 + 2.5 20th H + 22nd II 30th H + 7th II 30th H + 27th II 25th H + 15th II 11th H + 16th II 24th H + 36 II 13th H + 67 2.0 + 2.5 10th H + 25th II 25th H + 78 II 18th H + 31st II 20th

continuation of the table

1 2 3 4 H + 69 II 28th H + 3 n 26th H + 79 II 30th H + 80 II 30th H + 32 II 24th H + 37 II 24th H + 19th II 25th H + 43 II 30th H + 63 II 20th H + 18th II 13th H + 29th II 20th H + 33 II 20th H + 39 II 20th H + 41 II 20th H + 64 II 20th H + 66 II 15th H + 73 II 25th H + 85 II 20th H + 74 II 25th H + 127 2.0 + 1.0 30th

continuation of the table

1 2 3 4 H + 89 2.0 + 2.5 30th H + 90 11th 50 H + 146 1 » 30th H + 9th 11th 40 H + 160 11th 60 H + 163 11th 30th H + 20th 11th 13th H + 21st 11th 22nd H + 47 11th 22nd H + 48 11th 7th H + 70 11th 10th H + 71 2.0 + 2.5 50 H + 76 11th 20th H + 68 11th 10th H + 72 11th 22nd H + 73 11th 40 H + 84 11th 35 H + 8th 11th 30th H + 75 11th 50 H + 59 11th 20th

continuation of the table

1 2 3 4 H + 83 28th H + 52 60 H + 5 22nd H + 77 20th H + 81 30th H + 92 40 H + 91 40 H + 88 50 H + 86 40 H + 87 20th H + 96 40 H + 100 40 H + 103 30th H + 102 40 H + 104 50 H + 106 50 H + 107 50 H + 110 48 H + 111 50 H + 116 20th

continuation of the table

1 2 3 4 H + 118 n 30th H + 113 60 H + 115 «1 40 H + 117 lt 18th H + 119 fl 50 H + 120 II 20th H + 137 II 25th H + 138 II 25th H + 139 If 25th H + 141 2.0 + 2.5 40 H + 142 If 30th H + 143 lt 40 H + 133 If 50 H + 134 If 50 H + 135 If 50 H + 148 lt 20th H + 149 If 55 H + 11c If 40 H + 11b If 25th H + 150 II 35

continuation of the table

1 2 3 4 H + 151 30th H + 152 50 H + 153 27th H + 154 27th H + 155 50 H + 156 25th H + 157 43 H + 158 20th H + 171 20th

Explanations

TA = Ttriticum aestioum

a.m. = active substance

H = Phenoxaprop-ethyl = 2- / 4- (6-chlorobenzoxazol-2-yloxy) phenoxy) propanoic acid ethyl ester example

Wheat and two weeds Alopecurus myoruoides in 9 cm diameter pots, soil and grown under shrub

Avena fatua was sown in a clay-sand orangery filled with cold formation; the plants were then treated with the corresponding compounds of the invention. The formulations were applied in the form of aqueous suspensions or emulsions (application rate 300 L / ha) in combination with a herbicide (tank mix).

Growth changes and lesions of 5 test plants were evaluated 4 weeks after treatment.

The data in Table 2 show that the compounds of the present invention exhibit very good properties as antidotes and can effectively eradicate damage to crop plants such as wheat by exposure to herbicides; they do not reduce herbicide activity against weeds.

Thus, mixtures of the herbicides and the corresponding compounds of the invention can be used for selective weed control.

table

Mixture a.m. dose, Wheat Herbicidal activity Herbi- Eg. kg / ha Eg % damage %, with respect to cidas H no. H + No. (TA) ALM AVF 1 2 3 4 5

H + 0.8 0.4 52 40 100 100 0.2 18th 98 100 H + 7th 0.8 + 0.4 2 - - 0.4 + 0.2 0 100 100 0.2 + 0.1 0 98 100

continuation of the table

1 2 3 4 5 H + 27th VI 2 - - 0 100 100 0 99 99 H + 15th VI 2 - - 0 100 100 0 100 - H + 16th vv 1 - - 0 100 100 0 98 98 H + 18th IV 3 - - 0 100 100 0 100 97 H + 37 IV 2 - - 0 100 100 0 99 100 H + 36 0.8 + 0.4 2 - - 0.4 + 0.2 0 100 100 0.2 + 0.1 0 97 100 H + 73 IV 2 - - 0 100 100 0 100 100

continuation of the table

1 2 3 4 5 H + 67 IV 2 - - 0 100 100 0 100 100 H + 22nd lt 2 - - 0 100 100 0 100 99 H + 79 1 « 3 - - 2 100 100 0 98 98 H + 80 11th 4 - - 2 100 100 0 98 100 H + 68 VI 0 - - 0 100 100 0 99 97 H + 18th II 2 - - 0 100 100 0 100 97

ALM = Alopecurus myoruoides AVF = Avena fatma H = cf. See Table 1.

example

The barley (Oriol cultivars) was sown in 13 cm diameter cups filled with clay-sand soil and grown under open soil conditions until the start of scrub formation, after which the plants were treated with a mixture (Tankmix) consisting of the herbicide and the compound of the invention. The formulations were used in the form of aqueous emulsions or suspensions; application rate - 300 1 / ha.

Growth abnormalities and other lesions were evaluated 2 weeks after treatment.

The results in the Table show that the corresponding compounds of the present invention exhibit very good properties as antidotes and can effectively eliminate the effects of herbicides on crop plants such as barley; they do not reduce herbicide activity against weeds.

table

Compound Dose Herbicidal activity,%

Hey + E.g. No.a.m. kg / ha_HV

H! 3, 0 30th 1.5 13th Η _ς + 36 3.0 + 0.3 15th 1.5 + 0.15 3

Abbreviations: HV = Modeum Vulgare

H, = Diclofop-methyl (2- / 4- (2,4-dichlorophenoxy) -phenoxy / propionic acid methyl ester)

Claims (1)

A method for protecting crop plants from the adverse phytotoxic effects of herbicides, wherein the plants, plant seeds or cultivated soil are treated with an effective amount of a compound of formula (I) Z are identical or different substituents which can be halogen, nitro, cyano, trifluoromethyl residue Οχ - ,, - alkyl moieties of C _L or C ₄ -alkoxyl _L _ ₄ -alkiltiogrupės wherein the alkyl, alkoxy, and the substituents may be alkiltiogrupėse such as one or more halogen atoms, especially fluorine and chlorine; C ₃ _ ₆ cycloalkyl residues which may be C _{x. 4-} alkyl substituents; phenyl and phenoxyl residues which may be substituted, such as one or more halogen atoms and / or one trifluoromethyl residue; Y is hydrogen, C ₁ . ₄ alkyl residue, wherein the hydrogen can be completely or partly replaced by halogen and / or substituted with one substituent such as a C ₁ _ ₄ -alkoxyl residue or a C₁--alkiltiogrupė; C ₂ . ₆ alkenyl moiety C ₂ _ ₆ alkynyl moiety C _{3rd 6} cycloalkyl residue, which can be C ₁ _ ₄ alkyl optionally substituted and / or dichlorovinyl moiety; X is a hydroxyl group, a C ^ -alkyl radical, C ₃ _ ₆ cycloalkoxy moiety phenylalkoxy moiety 1-6 C-atoms, alkoxy moiety, phenoxy moiety, C ₂ _ ₆ -alkeniloksilo residue C _{7th b} -alkynyloxyl residue, C _x . _{A 6-} alkoxyl residue, a C 1-6 alkylthio group, wherein the alkoxyl residue or alkylthio group may be C ₁ . _2- alkoxyl substituents, mono- and dialkylaminocarbonyl moiety having 1-4 C atoms in the alkyl moiety, phenylaminocarbonyl moiety, N-alkylphenylaminocarbonyl moiety having 1-4 C atoms in the alkyl moiety, mono- or dialkylamino moiety having 1-6 C- atoms in the alkyl moiety, the alkylcarbonyloxy moiety having 1-6 Catomus in the alkyl moiety, C ₁ . _2- alkylthio, cyano or halogen; a residue of the formula < ^z ) n or NII / V wherein R is hydrogen or C 1-6 alkyl, a mono- or dialkylamino group containing a moiety, a cycloalkylamino group, a piperidine residue, a morpholino moiety Alkyl having 1-4 C atoms having 5-6 C atoms, a residue or 2,6-dimethylmorpholine residue; residue whose formula -O / V * = C R * «· 1. 2 wherein R and R may be identical or skiurtingi and are C ₁ _ ₄ alkyl radical or R ¹ and R ² may together form a cycloalkyl group of 5, 6 or 7 carbon atoms; on is 0, 1, 2 or 3, or, when X = OH, the salts of this compound used in agriculture, before, after or together with a herbicide belonging to the phenoxyphenoxy or heteroaryloxyphenoxycarboxylic acid ester group.