HU181621B - Herbicide compositions containing at least two different type active agents of the group of thiolcarbamate-, chloroacetanilide-, triasine-and urea-type herbicides,and dichloro-acetamide-type antidotum - Google Patents

Description

(54) Herbicides containing at least two different types of herbicides thiolcarbarnate, chloroacetanilide, Iriazine and urea as herbicides and dichloroacetamide type antidotes

The present invention relates to herbicidal compositions having a reduced phytotoxicity which:

(a) Chloroacetanilide herbicides of general formula (IV):

R ⁶ is hydrogen or C 1-4 alkyl;

R ⁷ is hydrogen or C 1-6 alkyl;

A is (1-4C) alkyl, (1-4C) alkyl (1-4C) alkynyl, (1-4C) alkylene or (1-4C) alkylene-carbonyl;

m is 0 or 1; and

B is C 1-5 alkyl or 1,3-dioxolan-2-yl and urea-type herbicides of formula VI

R is phenyl optionally substituted with one or more halo and / or C 1-4 alkyl and / or C 1-4 alkoxy or halo substituted phenoxy or trifluoroethoxy groups; benzothiazol-2-yl; C3-8cycloalkyl or 5- (C1-6alkyl) -1,3,4-thiadiazol-2-yl;

R ^{1 is} hydrogen, C 1-4 alkyl or C 1-4 alkoxy benzoyl;

R ¹³ is hydrogen, C 1-4 alkyl or phenyl;

R ^{14 is} hydrogen; Represents a (1-6C) alkyl, a (1-4C) alkoxy or (2-5C) alkynyl - or

(b) thiolcarbamate-type herbicides of general formula II:

R ³ and R ⁴ each independently represent C 1-6 alkyl; or together form a hexamethylene group;

R ⁵ is C 1-4 alkyl, benzyl substituted with halo or C 1-4 alkoxy, or di- or trichlorallyl, and triazine herbicides of formula V

R ⁸ is halogen, C 1-4 alkoxy, (C 1-4 alkyl) mercapto or azido;

R ⁹ is (C 1-6 alkyl) amino or (C 1-4 alkoxy) (C 1-4 alkyl) amino; and

R '° represents a (C 1-6 alkyl) amino group or a (C 3 -C 4 cycloalkyl) amino group optionally substituted with cyano (C 1-4 alkyl) - or

c) Chloroacetanilide herbicides of formula IV wherein R ⁶ , R ⁷ , A, m and B are as defined above and Triazine herbicides of formula V181621

181 623 dec - wherein ^{R8, R9} and ^R10 are as defined above -, or

d) Chloroacetanilide of formula IV wherein R ⁶ , R ⁷ , A, m and B are urea of formula VI wherein R ¹ ', R ¹² , R ¹³ and R ¹⁴ are herbicides of the above-defined and triazine type of the general formula (V) wherein R ⁸ , R ⁹ and R ^{10 are} as defined above; obsession

e) a chloroacetanilide of formula IV wherein R ⁶ , R ⁷ , A, m and B are thiolcarbamate of formula II, wherein R ³ , R ⁴ and R ⁵ a herbicides of the above-defined and triazine type of the formula V wherein R ⁸ , R ⁹ and R ^{10 are} as defined above; obsession

f) chloroacetanilide of formula IV: wherein R ⁶ , R ⁷ , A, m and B are urea of formula VI, wherein R ¹¹ , R ¹² , R ¹³ and R ^{14 is} a herbicide of the above type and a thiol carbamate of formula II wherein R ³ , R ⁴ and R ^{5 are} as defined above; obsession

g) thiolcarbamate of formula II, wherein R ³ , R ⁴ and R ^{5 are} as defined above, and urea of formula VI, wherein R ¹¹ , R ¹² , R ¹³ and R ^{14 are} as defined above - (V) triazine of the formula: - wherein ^{R8, R9} and ^R10 are as defined above - herbicides; obsession

h) a chloroacetanilide of formula IV, wherein R ⁶ , R ⁷ , A, m and B are urea of formula VI, wherein R ¹¹ , R ¹² , R ¹³ and R ^{14 is} as defined above for the triazine compound of formula V wherein R ⁸ , R ⁹ and R ^{10 are for} the above meaning and for the thiolcarbamate of formula II for R ³ , R ⁴ and R ⁵ a containing a mixture of herbicides as defined above and further containing from 0.1 to 50% by weight of the herbicidal active compounds, in the case of mixtures (a), (b) and (c), of an antidote of formula (I) in which X is oxygen; or a sulfur atom; n is 0 or 1;

R ¹ and R ² may be the same or different and are hydrogen or C 1 -C 2 alkyl, or

R * and R ^{2 taken} together are a butylene or pentylene group, or a pentylene or hexylene group, mono- or di-substituted with methyl, provided that when n is 0, R ¹ and R ^{2 are other than} hydrogen or C 1-2 alkyl, ad), (e) and (h) an antidote of formula (I) wherein X is oxygen or sulfur; n is 0;

R ¹ and R ^{2 taken} together form a pentylene group optionally substituted with C 1 -C 4 alkyl, and the mixture of f) and g) is an antidote of formula I wherein X is O;

n is 0 and

R * and R ² together form a pentylene group, together with the herbicidal active compound mixture in an amount of from 2.5 to 90% by weight, based on the total weight of the composition, of at least one solid and / or liquid carrier - preferably natural or synthetic powder mineral or paraffin oil, and optionally a surfactant, preferably a fatty alcohol poly (glycol ether) or a fatty alcohol sulfonate.

The antidotes of formula I are novel compounds. A major advantage of their use is that they can be combined with a mixture of different types of herbicides to provide a broad spectrum weed control without the detrimental phytotoxic effects.

It is known from the literature and plant protection practice that compositions containing the chloroacetanilide herbicide are excellent in controlling monocotyledonous weeds, while their use is severely limited by the fact that they are often harmful to the crop crop to be protected. Their harmful effects also depend on the type of crop to be protected, the composition of the soil and its moisture content and the weather conditions. The composition of the soil also influences the herbicidal effect, since a higher dose of herbicide is required to achieve the same herbicidal effect on soil with higher organic matter content. Higher doses of herbicides are also required in areas heavily infected with weeds. For the first time in the USA, selective preservatives have been experimentally tested to prevent the harmful phytotoxic effects of chloroacetanilide herbicides on crop plants without affecting their herbicidal activity. These substances are called antidotes according to the Anglo-Saxon literature ("antidote"). The first patent-protected antidotes are disclosed in U.S. Patent 3,131,509. The patent proposes the addition of 1,8-naphthalenecarboxylic acid and its derivatives (e.g., anhydride, esters, amides) to the herbicidal active ingredient. In plant protection practice, only 1,8-naphthalenedicarboxylic anhydride (naphthalic anhydride) was used as a dressing, known as Protect. A further family of compounds that can be used as an antidote for chloroacetanilide herbicides are described in Hungarian Patent No. 165,736. These compounds are various acid amides of various secondary amines and heterocyclic amines containing nitrogen (also). Of these, only N-dichloroacetyl-N, N-diallylamine, code R-25788, has been used in plant protection practice. Other protective compounds are disclosed in U.S. Patent Nos. 2,747,814 and 2,402,983.

However, the known antidotes are only partially suitable for solving the multidirectional task, since the range of herbicidal agents that need to be reduced is extremely wide, but at the same time has different phytotoxic effects. There is no doubt that crop plants respond differently to the harmful effects of each herbicide, and that is why the reduction of the harmful effect with a compound developed for this purpose is limited.

The aim of our research aimed at reducing the phytotoxicity of herbicidal agents is to develop chemically novel compounds that can be prepared from cheaper raw materials and which are capable of reducing this adverse effect, and which provide an environmentally beneficial property and a more economical use of herbicides.

Our research focused on dichloroacetamide derivatives. We have succeeded in producing novel dichloroacetamide-type compounds which particularly reduce or completely eliminate the phytotoxic effect of chloroacetanilide-type herbicides on crop plants without diminishing their excellent herbicidal activity. The ar.tidotum active compounds we have developed can be applied either individually (as dressing or spray agents) or in combination with chloroacetanilide herbicides, so that they can be used to select the most economically viable plant protection technology in the given field of plant protection. Their use allows, depending on soil conditions and weed infestation, more than twice the usual herbicide doses to be used safely to ensure complete weed control. The wide range of antidote doses available allows for the selection of the most appropriate antidotes doses or herbicide-antidote combinations according to environmental conditions, weed infections, and crop sensitivity.

In the compositions of the present invention, the thiolcarbamate of formula (II), the chloroacetanilide (IV), the triazine (V), the urea (VI) and At least two and one antidote of formula (I) may be present from the group consisting of amino-6-tert-butyl-3-methyl-thio-4,5-dihydro-1,2,4-triazin-2-one herbicide. In the above formulas R "R _2, R ^3, R ^4, R ^5, R \ R ^7, R ^s, R ^9, R ^10, R ^n, R ^I? , R ¹³ , R ¹¹ , A, n, m, B and X have the meanings given above. Additional restrictions within this have already been provided.

Representative compounds of each type of herbicide are summarized in the following tables.

Table I Compounds of formula II

Trivial name ' Chemical name R ^s R ' R * EPTC S-ethyl N, N-dipropyl-thiol-carbamate ethyl propyl propyl vernolate S-propyl N, N-dipropylthiolcarbamate propyl propyl propyl Buiylate S-ethyl N, N-diisobutyl tioIkarbamát ethyl i-butyl i-Butyl cycloate S-ethyl-N-cyclohexyl-N-ethylthiolcarbamate ethyl cyclohexyl ethyl benthiocarb S- (4-chlorobenzyl) -N, N-diethyl-thiol carbamate 4-chlorobenzyl ethyl ethyl triallate S- (2,3,3-trichloro-allyl) -N, N-diizo- propyl thiolcarbamate 2,3,3-trichloroethane allyl i-propyl i-propyl molinate S-ethyl N, N-hexamethylenethiolcarbamate ethyl hexamethylene hexamethylene Ethiolate S-ethyl N, N-diethylformamide, -tioJkarbamát ethyl ethyl ethyl Methiobencare S- (4-methoxybenzyl) -N, N-diethyl- -tiolkarbamát 4-methoxybenzyl ethyl ethyl pebulate S-propyl N-butyl-N-ethyl-thiolcarbamate propyl butyl ethyl Diallate S- (2,3-dichloro-allyl) -N, N-diisopropyl- -tiolkarbamát 2,3-dichloro- allyl i-propyl i-propyl

II. Compounds of formula IV

A trivial name Chemical ncv R ^e R ⁷ THE m δ alachlor 2-chloro-2 ', 6'-diethyl-N- (methoxymethyl) - acetanilide 2-ethyl 6-ethyl CH 1 methyl propachlor 2-chloro-N-isopropyl-chloroacetanilide H H i-propyl 0 - metolachlor 2-Chloro-2'-ethyl-6'-methyl-N - [(1-methyl) -2- (methoxyethyl)] - acetanil 2-ethyl 6-ethyl 1-methyl- ethene 1 methyl 2-chloro-2 ', 6'-diethyl-N- (I, 3-dioxolan-2- -ylmethyl) acetanilide 2-ethyl 6-ethyl CH 1 1,3-dioxo- lan-2-yl Diethatino- -ethyl 2-chloro-2 ', 6'-diethyl-N- (ethoxycarbonyl methyl) acetanilide 2-ethyl 6-ethyl methylene carbonyl 1 ethyl acetochlor 2-chloro-2'-methyl-6'-ethyl-N- (ethoxy methyl) acetanilide 2-methyl 6-ethyl CH 1 ethyl dimethachlor 2-chloro-2 ', 6'-dimethyl-N- (2-methoxy- ethyl) -acctanilid 2-methyl 6-Methyl ethylene 1 methyl

-3181621

II. Continue Table

A trivial name Chemical name R * R ⁷ THE m B butachlor 2-chloro-2 ', 6'-diethyl-N- (butoxymethyl) - acetanilide 2-ethyl 6-ethyl CH 1 n-butyl • 2-chloro-2 ', 6'-dimethyl-N- (isopropoxy methyl) acetanilide 2-methyl 6-Methyl CH 1 i-propyl Delachlor 2-chloro-2 ', 6'-dimethyl-N- (isobutoxy methyl) acetanilide 2-methyl 6-Methyl CH 1 i-Butyl pretilachlor 2-chloro-2 ', 6'-diethyl-N- (2-isopropoxy ethyl) acetanilide 2-ethyl 6-ethyl ethylene 1 i-propyl Pyrnachlor 2-chloro-N- (l-methyl-2-propynyl) - acetanilide H H l-methyl-2- propynyl 0 - terbuchlor 2-Chloro-2'-methyl-6'-tert-butyl-N- (butoxymethyl) acetanilide 2-methyl 6-tert butyl CH 1 n-butyl

III. Compounds of formula V:

Trivial year Chemical name R ' R ' R j. atrazine 2 satin-4- (ethylamino) -6- (isopropylamino) -s-triazine cl ethylamino isopropylamino simazine 2-chloro-4,6-bis (ethylamino) -s- triazine cl ethylamino ethylamino Cyanazin 2-chloro-4- (ethylamino) -6- (cyano -propylamino) -s-triazine cl ethylamino cyano-propylamino Cyprazin 2-Chloro-4- (cyclopropylamino) -6- (isopropylamino) -s-triazine cl cyclopropylamino isopropylamino 2-chloro-4- (butylamino) -6-ethyl- amino) -s-triazine cl butylamino ethylamino Propazin 2-chloro-4,6-bis (isopropylamino) - s-triazine cl isopropylamino isopropylamino prometryn 2- (methylmercapto) -4,6-bis (iso- propylamino) -s-triazine methylmercapto isopropylamino isopropylamino terbutrin 2- (methylmercapto) -4- (ethyl- amino) -6- (tert-butylamino) - s-triazine methyl karkapto ethylamino butylamino 2-methoxy-4- (ethylamino) -6- - (tert-butylamino) -s-triazine methoxy ethylamino butylamino

ARC. spreadsheet

The active ingredient The active ingredient trivial name chemical name linuron N- (3,4-dichlorophenyl) -N'-methyl-N'-methoxy-urea (active ingredient of Afalon) Neburon N- (3,4-dichlorophenyl) -N'-methyl-N'-n-butyl-urea monolinuron N- (3-chlorophenyl) -N'-methyl-urea N'metoxi chlorbromuron N- [3-chloro-4- (bromophenyl)] - N '-methyl-N' -methoxyurea Anisuron N '- [3,4- (dichloro-phenyl)] - N' - [4- (methoxybenzoyl)] - N, N-dimethylurea benzthiazuron N- (benzothiazol-2-yl) -N-methylurea Buthiuron N '- [5- (butylsulfonyl)] - (l, 3,4-thiazol-2-yl) -N, N-dimethylurea buturon N '- (4-chlorophenyl) -N- (l-methyl-prop-2-ynyl) -N-methylurea Chloreturon N '- [3-chloro-4- (ethoxy-phenyl]) - N, N-dimethylurea Chloraxuron N '- [4- (4-chlorophenoxy) phenyl] -N, N-dimethyl-kaibamid chlortoluron N '- [3-chloro-4- (methylsulfonyl) phenyl] - N, N-dimethyl-urea

-4181621

ARC. Continue Table

The active ingredient The active ingredient trivial and name chemical name Cycluron N '-cycloctyl-N, N-dimethylurea Difenozuren N '-4- [4-methoxyphenoxy) phenyl] -N, N-dimethylcarbamide diuron N '- (3,4-dichlorophenyl) -N, N-dimethylurea Ethidimuron N '- [5- (ethylsulfonyl) -l, 3,4-thiadiazol-2-yl] -N, N-dimethylurea fenuron N, N-dimethyl-N '-phenylurea fluometuron N '- [3- (trifluoromethyl) phenyl] -N, N-dimethylurea Fluothiuron N- [3-chloro-4- (chloro-difluoromethyl) thiophenyl] -N ', N'-dimethylurea Isonoruron N '- (1- or 2-hexahydro-4,7-methancindamyl) -N, N-dimethylurea isoproturon N '- [4- (isopropyl) phenyl] - N, N-dimethylurea methabenzthiazuron N- (benzothiazol-2-yl) -N ', N'-dimethylurea Metobromurone N '- (4-bromophenyl) -N-methoxy-N-phenylurea metoxuron N '- [3-chloro-4- (methoxycarbonyl) phenyl] - N, N-dimethylurea monuron N '- (4-chlorophenyl) -N, N-dimethylurea nonurban N '- (hexahydro-4,7-metanoindan-5-yl) -N, N-dimethyl-urea Parafluron N '- (4-Methanesulfonyl-biphenyl-methylphenyl) -N, N-dimethylurea Phenobenzuron N-benzoyl-N '- (3,4-dichlorophenyl) -N, N-dimethylurea siduron N- (2-methylcyclohexyl) -N'-phenylurea tebuthiuron N ', N'-dimethyl-N- (5-tert-butyl-l, 3,4-thiadiazol-2-yl) urea Tetrafluron N, N-dimethyl-N '- [3- (l, l, 2,2-tetrafluoroethoxy) phenyl] urea Thiazafluoron l, 3-dimethyl-l- (5-trifluoromethyl-l, 3,4-thiadiazol-2-yl) urea Thiadiazuron N-phenyl-N '- (l, 2,3-thiadiazol-5-yl) urea

The antidotes of the present invention can be summarized in Table V, together with their physical constants, in general formula I; X, n, Rj and R ₂ are listed above. meaning. Some antiV. spreadsheet

Serial number of compound X n ^R i R ₂ Name of the compound Physical constant First oxygen 0 pentylene N- (dichloroacetyl) -l-oxa-4-azaspiro [4.5] - -dean 105: δΙΟ? C Second oxygen 0 1'-methylpentylene N- (dichloroacetyl) -10-1-oxa-4-aza-spiro [4,5] decane Mp 100-102 ° C Third oxygen 0 3'-methyl-pentylene N- (dichloroacetyl) -8-methyl-l-oxa-4-azaspiro - [4.5] decane 119-120 ° C 4th oxygen 0 l ', 5'-dimethyl- pentyl N- (dichloroacetyl) -6, l0-dimethyl-1-oxa-4-aza- spiro [4.5] decane n ": 1.5217 5th oxygen 0 butylene N- (dichloroacetyl) -l-oxa-4-azaspiro [4.4] - nonane M.p. 79-80 ° C 6th oxygen 0 hexylene N- (dichloroacetyl) -l-oxa-4-azaspiro [4.6] - undecane M.p. 81-82 ° C 7th sulfur 0 pentylene N- (dichloroacetyl) -l-thia-4-azaspiro [4.5] - -dean 149-151 ° C 8th sulfur 0 1'-methylpentylene N- (dichloroacetyl) -10-methyl-l-thia-4-azaspiro - [4.5] decane 106-109 ° C 9th sulfur 0 3'-methyl-pentylene N- (dichloroacetyl) -8-methyl-l-thia-4-azaspiro - [4.5] decane 127-129 ° C 10th sulfur 0 butylene N- (dichloroacetyl) -1-thia-4-aza-spiro [4,4] nonane M.p. 83-850 ° C 11th sulfur 0 hexylene N- (dichloroacetyl) -l-thia-4-azaspiro [4.6] - undecane 96-99 ° C 12th oxygen 1 hydrogen hydrogen N- (dichloroacetyl) tetrahydro-1,3- [2H] oxazine ng: 1.5168 13th oxygen 1 methyl methyl N- (dichloroacetyl) -2,2-dimethyl-tetrahydro-3- - [2H] oxazin n ": 1.5070 14th oxygen 1 methyl methyl N- (dichloroacetyl) -2-methyl-2-ethyl-tetrahydro- -l, 3- [2H] oxazin n ² D ^s : 1.4919

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Continuation of Table V

Serial number of compound X n R, R ₂ Name of the compound Physical constant 15th oxygen 1 pentylene N- (dichloroacetyl) -l-oxa-5-aza-spiro [5.5] - undecane M.p. 111-112 ° C 16th oxygen 1 1'-methylpentylene, N- (dichloroacetyl) -ll-methyl-l-oxa-5-aza- spiro [5.5] undecane 135-138 ° C 17th oxygen 1 3'-methyl-pentyl N- (dichloroacetyl) -9-methyl-l-oxa-5-aza-spiro - [5.5] undecane 115-118 ° C 18th oxygen 1 butylene N- (dichloroacetyl) -l-oxa-5-aza-spiro [5.4] - -dean Mp 62-64 ° C 19th oxygen I hexylene N- (dichloroacetyl) -l-oxa-5-aza-spiro [5.6] - dodecanetriyl n ² D ⁶ : 1.5012

Table V shows that most of the new derivatives are solid, crystalline compounds, only some of which are liquid at room temperature.

The compounds of formula (1) can be prepared by methods known in the art for the preparation of the acid amide type compounds. The most common of these is the acylation of a cyclic amine of formula (III), as defined above, R ₁ , R ₂ , X and Na, or a salt thereof, with dichloroacetic acid, its chloride, anhydride or ester optionally in an inert solvent. No. 547 and 2,350,800. German Patent Specification; WR Vaughan et al., J. Org. Chem. 26, 145-8 (1961)], Suitable inert solvents include a ketone (e.g. acetone, methyl ethyl ketone) or an aliphatic hydrocarbon (e.g. hexane) or an aromatic hydrocarbon (e.g. benzene, toluene, xylene, chlorine). benzene, nitrobenzene), but diethyl ether or dimethyl sulfoxide or a chlorinated aliphatic hydrocarbon (e.g., methylene chloride, carbon tetrachloride) may be used. The acylation can also be carried out with their inert solvents.

Organic bases (e.g., triethylamine, trimethylamine, pyridine, N, N-dimethylaniline) may be used as the acid scavenger, or inorganic bases (alkali metal carbonates, alkaline bicarbonates, alkaline bases or aqueous solutions thereof) may also be used. The acylation temperature may be from -50 ° C to 160 ° C, preferably from -20 ° C to 40 ° C.

The starting amines of formula (III) are five- or six-membered heterocyclic compounds containing one nitrogen atom and one oxygen or sulfur atom, the preparation of which has been described in more detail in the literature (e.g., ED Bergman et al., J. Am. Chem. Soc. 358-61 (1953); J. B. Doughly, et al., J. Am. Chem. Soc., 72, 2866-6 (1950); W. H. Wateuebe, J. Am. Chem. Soc. 79, 2833-6 (1957). Both five-membered and six-membered cyclic amines can be prepared by reacting the corresponding hydroxyalkylamine or mercaptoalkylamine or its hydrochloride with the corresponding carbonyl compound in a solvent, in the presence or absence of a catalyst, at room temperature or at elevated temperature. with or without withdrawal. Suitable catalysts are basic catalysts (e.g. alkali metal carbonates) or acidic catalysts (e.g. hydrogen6).

chloride, hydrobromic acid, p-toluenesulfonic acid). Suitable solvents are aliphatic hydrocarbons (e.g. hexane, petroleum ether), their halogenated derivatives (e.g. methylene chloride, carbon tetrachloride), aromatic hydrocarbons (e.g. benzene, toluene, xylene) or their derivatives (e.g. chlorobenzene, nitro). benzene), but also ethers or excess carbonyl reactants. The reaction temperature may range from 20 to 200 ° C. In this way, five-membered cyclic amines can be prepared by reacting aziridine with a corresponding carbonyl-containing compound in the presence of hydrogen sulfide.

In another embodiment of the compounds of formula I, N-dichloroacetylated hydroxyalkylamine or mercaptoalkylamine or their hydrochlorides are reacted with the corresponding carbonyl-containing compound under the reaction conditions already detailed. Another possibility is to react the N-nitroso derivative of the corresponding heterocyclic amines with dichloroacetyl chloride (US Patent No. 2,035,796; KL Hebenbrock & al., Justus Liebig, Ann. Chem. 1972, 765, 78-7). 93).

The N-acylated heterocyclic amides can also be prepared by reacting Schiff base formed from the corresponding amino alcohol and carbonyl-containing compound with dichloroacetyl chloride under the reaction conditions detailed above [M. Businelli: 11, Farmaco (Pavia) Ed. Sci., 10, 127-34 (1955)].

The preparation of compounds of formula I is illustrated by the following examples.

Example 1

Preparation of N- (dichloroacetyl) -1-oxa-4-azaspiro [4,5] decane (Compound 1) g (0.645 mol) of cyclohexanone and 30 g (0.491 mol) of ethanolamine of benzene is heated to reflux until 8.8 ml of water is distilled off. After cooling, 55 g of 40 weight ⁰ /, - an aqueous sodium hydroxide solution (0.55 mol) is added, and with external cooling with ice-salt (0.5 mol) of dichloroacetyl chloride was added dropwise to 74 g into it. At the end of the addition two at room temperature

After stirring for -6181621 hours, the mixture was washed first with hydrochloric acid and then with water until neutral. The benzene is then evaporated in vacuo. 10 g (0.4 mol) of a greenish white crystalline solid are obtained, which is abs. Recrystallization from ethanol gave a white crystalline product, m.p. 105.5-107 ° C. The structure of the compound is confirmed by its IR spectrum.

Analysis:

Calculated: C 47.63%; N, 5.50%;

Cl, 28.12% by weight;

Found: C, 47.12%; N, 5.70%;

Cl, 28.56% by weight.

Example 2

Preparation of N- (Dichloroacetyl) -1-thia-4-azaspiro [4,5] decane (Compound 7)

9.8 g (0.1 mole) of cyclohexanone and 7.7 g (0.1 mole) of 2-mercaptoethylamine in 100 ml of benzene are heated to reflux until the water is removed continuously.

1.8 ml of water distil off. The reaction mixture was then cooled and treated with 11 g of 40% w / w aqueous sodium hydroxide solution and 14.7 g (0.1 mol) of dichloroacetyl chloride was added dropwise under external brine. After the addition was complete, the reaction was allowed to proceed at room temperature for two hours. The mixture is then washed first with hydrochloric acid and then with water, and the benzene is distilled off in vacuo. 17.2 g (0.064 mol) of a white powdery solid are obtained, which is abs. Recrystallization from ethanol gave a white crystalline solid, m.p. 149-151 ° C. The structure of the compound is confirmed by its infrared spectrum.

Analysis:

calcd: C, 44.77% w / w; N, 5.22% by weight;

S 11.95 wt%, Cl 26.42 wt%;

Found: C, 44.51%; N, 5.31%;

S 12.11% by weight, Cl 26.25% by weight.

Example 3

Preparation of N- (Dichloroacetyl) -8-methyl-1-oxa-4-azaspiro [4,5] decane (Compound 3)

4-Methylcyclohexanone (11.2 g, 0.1 mol) and ethanolamine (6.1 g, 0.1 mol) in benzene (100 ml) were heated to reflux until the water was removed continuously.

1.8 ml of water distil off. The reaction mixture was cooled and pyridine (8 g, 0.1 mol) was added and dichloroacetyl chloride (14.7 g, 0.1 mol) was added dropwise under external brine. Further, Example 2 gave 20.7 g (0.078 mol) of a pink ointment which was recrystallization from ethanol gave a white crystalline solid, m.p. 119-120 ° C. The structure of the compound is confirmed by its infrared spectrum.

Analysis:

Calculated: C 49.63%; N, 5.26%;

Cl 26.64%;

Found: C, 49.45%; N, 5.35%;

Cl, 26.92% by weight.

example

Preparation of N- (Dichloroacetyl) -1-oxa-5-aza-spiro [5,5] -undecane (Compound 15)

17.6 g (0.18 mol) of cyclohexanone and 11.2 g (0.15 mol) of 3-aminopropanol in 50 ml of benzene are refluxed until 2.7 ml of water are distilled off. The reaction mixture was cooled, 16 g of 40% w / w (0.165 mol) aqueous sodium hydroxide solution was added and 22.1 g (0.15 mol) of dichloroacetyl chloride was added dropwise thereto.

Further, Example 2 gave 15.7 g (0.059 mol) of an off-white crystalline solid, which was recrystallized from ethanol to give a white crystalline solid. M.p. 111-112 ° C.

Its structure is evidenced by its infrared spectrum.

Analysis:

calcd: C, 49.63% w / w; N, 5.26%;

Cl 26.64%;

Found: C, 49.52% w / w; N, 5.32%;

Cl, 26.45% by weight.

Example 5

Preparation of N- (Dichloroacetyl) -1-thia-4-aza-spiro [4,4] nonane (Compound 10)

8.4 g (0.1 mole) of cyclopentanone and 7.7 g (0.1 mole) of 2-mercaptoethylamine in 100 ml of benzene are heated to reflux until the water is removed continuously.

1.8 ml of water are distilled off. The reaction mixture was then cooled, pyridine (8 g, 0.1 mol) was added, and dichloroacetyl chloride (14.7 g, 0.1 mol) was added dropwise under external salt-ice cooling.

In the same manner as in Example 2, 21.6 g (0.085 mol) of a yellowish ointment remain, which is recrystallized from n-hexane. A white crystalline solid is obtained, m.p. 83-85 ° C. The structure of the compound is confirmed by its infrared spectrum.

Analysis:

calcd: C, 42.52% w / w; N, 5.51%;

S, 12.61% w / w; Cl, 27.89%;

Found: C 42.35 weight ⁰ /, ',; N, 5.45%;

S, 12.80% w / w; Cl, 27.56% by weight.

The other compounds of formula (I), described in Table I, may be prepared in a similar manner to the examples described and their physical constants (melting point or refractive index) are included in the table.

Example 6

Preparation of N-dichloroacetyl-1-oxa-4-azaspiro [4,5] decane (Compound No. 1)

14.12 g (0.1 mol) of the 1-oxa-4-aza-spiro [4,5] decane obtained as an intermediate in Example 1 are dissolved in 50 ml of methylene chloride and 10.2 g (0 Triethylamine (1 mol) and dichloroacetyl chloride (14.8 g, 0.1 mol) were added dropwise under ice-cold cooling. After the addition was complete, the reaction mixture was stirred for 2 hours

Stir at -7181621 at room temperature. The resulting triethylamine hydrochloride is then washed with water, the methylene chloride solution is washed neutral with water, dried over anhydrous sodium sulfate, and the solvent is evaporated off under vacuum. A tan solid weighing 17.6 g (0.069 mol) was obtained. The crude product is abs. Recrystallization from ethanol gave a white crystalline product, m.p. 105.5-107 ° C. The structure of the compound is confirmed by its IR spectrum.

Example 7

Preparation of N- (dichloroacetyl) -1-oxa-4-aza-spiro [4,5] decane (Compound No. 1)

17.2 g (0.1 mole) of N- (dichloroacetyl) ethanolamine, 11.8 g (0.12 mole) of cyclohexanone and 0.2 g of p-toluenesulfonic acid in 100 ml of toluene are formed continuously. distill until 1.8 mL (0.1 mol) of water is distilled off. The reaction mixture was cooled, washed neutral with water, dried over anhydrous sodium sulfate, and the solvent was evaporated in vacuo. The resulting slightly fluffy product is washed with hexane

18.2 g (0.072 mol) of a tan solid are obtained. The material is abs. Recrystallization from ethanol gave a white crystalline product, m.p. 105-106.5 ° C. The structure of the compound is confirmed by its IR spectrum.

Example 8

Preparation of N- (Dichloroacetyl) -1-thia-4-aza-spiro [4,5] decane

Cyclohexanone (9.8 g, 0.1 mol) and 2-mercaptoethylamine (7.7 g, 0.1 mol) in benzene (100 ml) were heated to reflux until 1.8 ml of water was distilled off. After cooling to room temperature, phosphorus trichloride (5.5 g, 0.04 mmol) was added, followed by dichloroacetic acid (12.9 g, 0.1 mol) and refluxed for 3 hours. The hot solution was decanted from the sticky precipitate on the wall of the flask, cooled and washed with sodium bicarbonate solution, then water to neutral, then dried over anhydrous sodium sulfate. The solvent was evaporated in vacuo to give 16.8 g (0.063 mol) of a yellowish-white amorphous substance which was abs. Recrystallization from ethanol gave a white crystalline solid, m.p. 149-151 ° C. The structure of the compound was confirmed by its infrared spectrum.

The dichloroacetamide derivatives of the formula (I), either alone or in combination with a herbicidal active ingredient, can be formulated in powder or liquid formulations using known and conventional techniques for pesticides. For example, the crystalline materials from the compounds of formula (I) may be formulated into a wettable powder formulation according to the following formula:

70.0% by weight No. 7 compound,

17.0% by weight kaolin,

8.0% by weight of active silica,

2.5 wt / ír fatty alcohol sulphonate,

2.5 w / w lignin sulfonic acid sodium.

The components blended in the above ratio are ground in an Alpine mill to provide a usable wettable powder. When formulated together with the herbicidal active ingredient, the composition should be different from, for example, 50% by weight of the herbicidal active ingredient and 20% by weight of the compound of formula (I) with the additives. Additives that can be used in wettable powder formulations include diluents of mineral origin, such as adhesives. If it is desired to reduce the phytotoxicity of known herbicidal agents by treating the seed of the crop with a compound of formula (I) prior to sowing, it is formulated with a carrier of 20 to 30% by weight, preferably talc.

Some of the compounds of formula (I) are liquid at room temperature and are preferably formulated in concentrates using, for example, an emulsion-forming agent;

20-50 weight '/ no. compound

74-45% by weight xylene,% by weight polyoxyethylene alkyl ether emulsifier.

Of course, an emulsion concentrate can also be prepared for the crystalline compounds, and this is particularly advantageous if the herbicidal active compounds which are intended to be harmed by the compound of the formula I are in liquid form.

Particularly preferred formulations comprising a plurality of herbicidal active ingredients are those having as herbicidal component a chloroacetanilide and a urea or a chloroacetanilide, a urea and a triazine or a thiolcarbamate, a urea and a triazine or containing a combination of a thiolcarbamate, a chloroacetanilide, a urea and a triazine herbicide. In each case, the weight ratio of the herbicidal compounds to each other preferably ranges from:

chloro-acetanilide + urea derivative: 1-1: 2 chloroacetanilide + urea + triazine derivative: 1: 1-1: 2: 4 thiolcarbamate + urea + triazine derivative

20: 1: 1-1: 2: 5 thiolcarbamate + chloroacetanilide + urea +

The iriazine derivative I is 10: 1: 1: 1 to 1: 10: 5: 5

The herbicidal compositions, the total drug concentration in each case is 2.5 to 90 weight ⁰ / range.

The following formulation examples illustrate the composition of some representative formulations of the compositions of the invention.

Example T.

Wettable powder formulation

1. S- (4-chlorobenzyl) -N, N-diethylthiol carbamate 10% by weight

2-Chloro-4,6-bis (isopropylamino) -1,3,5-triazine 50 w / w antidote: no. Compound 0.1% by weight emulsifier: fatty alcohol sulfonate (Arkopon T, Hoechst) 5% by weight

-8181621

dispersant: sodium lignin sulfonate kaolin 3% by weight 31.9% by weight 100% ° / " 2. S-propyl-N, N-dipropyl-thiolcarbamate 65% by weight 2-Chloro-N-isopropylacetanilide 2-Chloro-4- (ethylamino) -6- (isopropyl) 5% by weight amino) -1,3,5-triazine 1 dumbbell antidote: no. Compound Emulsifier: Polyoxyethylene alkyl aryl ether (Atlox 1690, Atlas 4% by weight Chemie) dispersant: sodium lauryl 4% by weight -sulfate 3% by weight colloidal synthetic silica 10% by weight vermiculite 3. 2-Chloro-2 ', 6'-diethyl-N- (methoxymethyl) - 8% by weight 100 / ° acetanilide 2-methoxy-4,6-bis (ethylamino) -l, 3,5- 8% by weight triazine 40% by weight antidote: no. compound emulsifier: poly (ethylene oxide) - 10% by weight -lauryl ether (Brij 30, Atlas Chemie) dispersant: calcium lignin 5% by weight sulfonate 3% by weight colloidal synthetic silica 20% by weight kaolin Example 11 Aqueous colloidal suspension formulation 14% by weight 100% by weight S-ethyl-N, N-dipropylthiolcarbamate 3 weight / h 2-chloro-N-isopropylacetanilide 2-chloro-4- (l-cyano-l-methyl-ethylamino) - 40 weight ° / " -6-ethylamino-1,3,5-triazine 15% by weight antidote: no. compound 5% by weight emulsifier: fatty alcohol-poly-glycol- ether (Emulsogen M, Hoechst) dispersant: sodium alkyl- 4 weight ° / ₀ -sulfate 3 weight / h protective colloid: lecithin 1 weight / h colloidal synthetic silica 4 wt / h WATER 25 wt / h 100 wt% 2. S-ethyl-N, N-dipropylthiolcarbamate 2-chloro-2'-ethyl-6'-methyl-N- (1-methyl-2- 20% by weight methoxyethyl) acetanilide 2-chloro-4-ethylamino-6-isopropylamino 20 wt / h 1,3,5-triazine 10% by weight antidote: no. compound 10 wt / h emulsifier: polyoxyethylene alkyl · -phenyl ether (Atlox 1690, Atlas Chemie) dispersant: potassium lignin 5% by weight sulfonate 3 weight / h protective colloid: lecithin 1 weight / h colloidal synthetic silica 6 weight / h WATER 25 dumbbells

100% by weight

NI. example

Colloidal oily suspension formulation

S-propyl N, N-dipropylthiocarbamate 2-chloro-2'-methyl-6'-ethyl-N- (ethoxymethyl) - 10% by weight acetanilide 2-chloro-4,6-bis (ethylamino) -1,3,5 5 wt / h triazine 3% by weight antidote: no. compound 9 wt / h emulsifier: fatty alcohol poly (glycol ether) and ethylene oxide-propylene oxide polymerization product (GENAPOL PF10, Hoechst) 7% by weight paraffin 66 wt / h 100 wt / h S-ethyl-N, N-dipropylthiolcarbamate 2-chloro-2'-methyl-6'-ethyl-N- (ethoxymethyl) - 45 weight / h acetanilide) 2-chloro-4- (ethylamino) -6-isopropylamino 30 weight / h 1,3,5-triazine 10 wt / h antidote: no. Compound Emulsifier: Polyoxyethylene-aryl 8 wt / h ether (Pycal 94, Atlas Chemie) dispersant: sodium lauryl 5 wt / h sulfate ARC. example Granule preparations 2 weight / h 100 weight / h S-ethyl N, N-dipropylthiolcarbamate 2-chloro-2 ', 6'-diethyl-N- (butoxymethyl) - 1 weight / h acetanilide 2-chloro-4- (eti1-amino) -6-isopropyl- 1 weight / h amino-l, 3,5-triazine 0.5 wt / h antidote: no. compound 1.25 wt / h attapulgite Example V Wettable powder preparations 96.25 weight / h 100 weight / h 2-chloro-N-isopropylacetanilide N- (3-chloro-4-bromophenyl) -N'-methyl 85 wt / hr -N'-methoxyurea 4.25 wt / h antidote: no. compound 0.1 wt / hr emulsifier: fatty alcohol sulphonate dispersant: sodium lignin 4 wt / h sulfonate 3 weight / h kaolin 3.65 wt / hr ] 2-chloro-2 ', 6'-diethyl-N- (methoxymethyl) - 100 wt / hr acetanilide N- (4-trifluoromethyl-phenyl) -N ', N' 10 wt / h dimethyl-urea 2- (methylthio) -4- (ethylamino) -6- (tert 20 wt / h butylamino) -l, 3,5-triazine 40 wt / hr antidote: no. compound 5 weights ⁰ ',',

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emulsifier: polyoxyethylene alkyl ether (Atlox 4873, Atlas Chemie) dispersant: magnesium lauryl 4% by weight -sulfate 3 weights / ζ colloidal synthetic silica 8 weight / ζ montmorillonite 3. S- (4-methoxybenzyl) -N, N-diethyl- 10% w / w 100% w / w -tiolkarbamát 5 weight / / N-phenyl-N ', N'-dimethylurea 2-chloro-4- (cyclopropylamino) -6- (isopropyl 10 weight / / -amino) -1,3,5-triazine 25 weight / ζ antidote: no. Compound Emulsifier: Alkylphenylalkoxalate 20 weight ”/, (Emulsogen ICL, Hoechst) Dispersant: Sodium Lignin 6 weight / ζ sulfonate 4 weight / ζ colloidal synthetic silica 8 weight / ζ vermiculite 17% by weight 100% by weight

VI. example Aqueous colloidal suspensions 1. 2-Chloro-2'-methyl-6'-ethyl-N- (1-methyl-2-methoxy-ethyl) -acetanilide 40% by weight N- (3-chloro-4-methoxyphenyl) -N ', N' dimethylurea 2% by weight 2-chloro-4- (ethylamino) -6- (isopropyl amino) -l, 3,5-triazine 2 weight / ζ antidote: no. compound 6 weight / ζ emulsifier: polyoxyethylene sorbitan monolaurate (Tween 20, Atlas Chemie) 4 weight / ζ dispersant: potassium lignin sulphonate 1 weight / ζ protective colloid: lecithin 1% by weight colloidal synthetic silica 8% by weight WATER 36 weight / ζ 2. 2-Chloro-N-isopropylacetanilide 100 weight / ζ 10% by weight N- (4-bromophenyl) -N '-methoxy-N' -methylurea 20% by weight antidote: no. compound 10 weight / / emulsifier: mixture of polyoxyethylene alkyl ether and alkyl phenol alkoxalate (Emulsogen Ic, Hoechst) 6% by weight dispersing agent: sodium lauryl sulfate 3% by weight protective colloid: lecithin 1 weight / ζ colloidal synthetic silica 15 weight / ζ water 35 weight / / 3. S-ethyl-N, N-dipropylthiolcarbamate 100 weight / ζ 2% by weight 2-chloro-N-isopropylacetanilide 20 weight / ζ N- (3,4-dichlorophenyl) -N'-methyl-N-butylurea 10 weight / / 2-chloro-4- (l-cyano-l-methyl-ethylamino) -6-ethylamino-1,3,5-triazine 5% by weight 10

2-methylthio-4,6-bis (isopropylamino) - 1,3,5-triazine 5% by weight antidote: no. compound emulsifier: fatty alcohol sulfonate 5 weight / / (Arkopon T, Hoechst) 5 weight / / protective colloid: lecithin dispersant: sodium lignin 1 weight / ζ sulfonate 5% by weight colloidal synthetic silica 10% by weight WATER 4. 2-Chloro-2'-methyl-6'-ethyl-N- (ethoxymethyl) - 34% by weight 100% by weight acetanilide 4- (3-chloro-4-bromophenyl) -N'-methyl-N 10% by weight -methoxy-urea N- (4-isopropylphenyl) -N, N'-dimethyl- 10% by weight -urea 10% by weight antidote: no. Compound Emulsifier: Polyoxyethylene alkyl 10 weight / / aryl ether (Atlox 1690, Atlas Chemie) dispersant: lignin sodium 5% by weight sulfonate 4 weight / ζ protective colloid: lecithin 1% by weight colloidal synthetic silica 10% by weight water VII. example Oily colloidal suspensions 40 weight / ζ 100 weight / ζ 1. S-propyl N, N-dipropylthiolcarbamate S-chloro-2 ', 6'-diethyl-N- (ethoxycarbonyl). 2% by weight methyl) acetanilide 20 weights / » N-phenyl-N ', N'-dimethyl-urea 2-methoxy-4- (ethylamino) -6- (tert-butyl 10 weight / / amino) -l, 3,5-triazine 10 weight / / antidote: no. compound 8 weight / ζ emulsifier: a mixture of polyoxyethylene alkyl aryl ether and alkyl phenol alkoxalate (Emulsogen I-40, Hoechst) 7% by weight paraffin oil 43 weight / ζ 100 weight / ζ 2. S-ethyl-N, N-dipropylthiolcarbamate 40 weight / ζ S-ethyl N, N-diisobutyl thiolcarbamate 2-chloro-2 ', 6'-diethyl-N- (butoxymethyl) - 30 weight / ζ acetanilide 7 weight ⁰ /, N- (benzothiazol-2-yl) -N-methylurea 2-chloro-4- (ethylamino) -6- (isopropylamino) - 7% by weight 1,3,5-triazine 7 weight / ζ antidote: no. Compound Emulsifier: Polyoxyethylene alkyl 3 weights / ζ -aryl ether (Atlox 1690, Atlas Chemie) 6 wt / h 100 wt% 3. S-ethyl-N, N-dipropylthiolcarbamate 60% by weight N-phenyl-N ', N'-dimethylurea 2-chloro-4- (1-cyano-1-methylethylamino) -6- 3% by weight ethylamino-l, 3,5-triazine 3% by weight antidote: no. compound emulsifier: polymerization of alkylphenol alkoxalate and ethylene oxide-propylene oxide 5% by weight

-10181621 product mix (GENAPOL PF 20,

Hoechst) 5% by weight of petroleum jelly oil 24% by weight

100% by weight

VIII. example

Granular preparations

1. 2-Chloro-2'-methyl-6'-ethyl-N- (ethoxymethyl) -

acetanilide 1 weight% N- (3,4-dichlorophenyl) -N'-methyl-N'- -methoxy-urea 1 weight% antidote: no. compound 0.5 weight% attapulgite type material 97.5 weight% 100 weight% S-ethyl-N, N-dipropylthiolcarbamate 25 weight% 2-chloro-2 ', 6'-diethyl-N- (methoxymethyl) - acetanilide 5 weight% 2-chloro-4- (ethylamino) -6- (isopropyl amino) -l, 3,5-triazine 3 weight% antidote: no. compound 2 weight% attapulgite type clay 65 weight%

100% by weight

The phytotoxic activity of the heterocyclic dichloroacetamides of the formula I is exerted when applied together with the herbicidal active ingredients in the plant environment (either together or in the form of a spray mixture prepared before spraying) and even when spraying the herbicide. prior to treatment with antidotes. An economical and preferred method of treatment is to treat the seed with the compound of formula I before sowing and then spraying the herbicide on the soil immediately before or after sowing. The herbicidal agents may be formulated together and separately.

The phytotoxic activity of the antidotes of the present invention in combination with various herbicidal combinations is shown in the following biological examples.

Example A)

Biological impact assessment in a greenhouse (spraying)

The active compounds of the formula I according to the invention are various compositions of the chloroacetanilide type IV herbicides and the urea type VI herbicides and the triazine type herbicides V and the thiolcarbamate herbicides II Greenhouse studies were performed to investigate the effects of the mixtures of the mixtures on the harmful phytotoxicity of crops.

The test herbicides were available in the form of a formulation by the manufacturer. The amounts needed for spraying were measured so that the calculated doses of the active ingredient in the table below were sprayed; (for example, for the herbicide S-ethyl-,9, Ν-dipropylthiolcarbamate, Eptam 6E emulsifiable formulation containing 76.9% w / w, 9.75 kg / ha is equivalent to 12.68 kg / ha Eptam 6E) 5 kg / ha of Acetochlor 50 EC in emulsifiable formulation containing 2% chloro-2'-methyl-6'-ethyl-N-ethoxymethylacetanilide containing 50% active ingredient corresponds to 10 kg / ha formulation dose the Hungazin PK 50 WP wettable powder formulation of 2-chloro-4-isopropylamino-6-ethylamino-1,3,5-triazine containing 50% by weight of the active ingredient has a dosage of 1.0 kg / ha corresponding to 2 kg / ha when applied at a dosage of 1.5 kg / ha of Dicuran 80 WP wettable powder formulation containing 80% by weight of the active ingredient N- (3-chloro-4-methylphenyl) -N ', N'-dimethylurea. 1.875 kg / ha formulation dose).

The active compounds represented by the general formula (I) of the present invention were used as wettable powders containing 70% by weight of the active ingredient and as an emulsifiable composition containing 50% by weight of the active ingredient as described in the formulation examples. Doses were chosen so that the doses of VI. correspond to the dose of active ingredient according to Table 1 (eg 1.44 kg / ha of the active ingredient dose of 70% by weight of wettable powder formulation is 1.44 kg / ha).

The experiments were carried out in 15 cm diameter pots, 5 replicates per experiment. The pots were filled with sandy loam soil up to 5 cm from the top of the pot, then 10 seeds of SC 3269 maize seed and sunflower seed were placed on top of the soil. The seeds were then covered with soil treated or untreated according to the experiment, 5 cm thick. The herbicide treatment was carried out by diluting the herbicidal formulations converted to the soil surface with water equivalent to 400 liters / ha of water and spraying the soil with an aqueous emulsion of the herbicide in a small mixer. The treated soil was immediately covered with seeds in the pots.

The method of combining herbicide-antidote treatment was the same as that of herbicides except that the amount of herbicide [substance of the formula (V) according to the invention] was sprayed with a mixture of 400 l / ha water and sprayed with mixing. while on the ground. Seeds prepared as described above were immediately covered with the treated soil in a 5 cm thick layer. For quantitative evaluation, untreated controls were set up in the same manner as the treated experiments in 5 replicates per crop with untreated soil.

The prepared pots were then kept in a greenhouse, watered as necessary. Evaluation was carried out 4 weeks after sowing. For evaluation, the plants were cut above the soil and weighed. Results are expressed as the mean of 6 replicates. The weight of the untreated control green plant was taken as 100% and compared to the weight of the treated plants. Our results in VI. are shown in the table.

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Example B)

Biological experiment in a greenhouse (dressing)

Greenhouse experiments were conducted to determine the extent to which the compounds of formula (I) of the invention reduced the chloroacetanilide herbicides (IV) and the urea (VI) and the triazine (V). The herbicides of different combinations of type II herbicides and thiolcarbamate type II herbicides are applied to the crop crop by seeding the seed of the crop with the compounds represented by the formula I and seeding the seed in the soil treated with the herbicide combination.

The experimental conditions and experimental setups were the same as for greenhouse spraying experiments, except that the soil was treated with herbicide only. The seed was treated with a wettable powder composition containing 70% by weight of the active ingredient or 50% by weight of an emulsifiable composition of the compounds of formula I according to the invention at the dose indicated in the attached table. For seeding, 100 g of seed was mixed in a 1-liter flask with the following dressing, elkc5:

Dose of 0.5 kg / q active ingredient 0.5 g of active ingredient per 100 g of seed. Based on this, 0.715 g of the wettable powder formulation containing 70% w / w of the active ingredient

1.5 ml of distilled water was mixed and the seeds were shaken in 10 flasks of the resulting suspension until the wall of the flask was clean. The seeds so treated were then placed in pots prepared as described above. As a comparative study, untreated controls were set for each crop at 5 replicates per crop. The prepared pots were kept in a greenhouse, watered as needed. After 4 weeks, the mature plants were cut above the soil and weighed. The results are given in 5 replicates. The weight of untreated control green20 plants was taken as 100%, and the green weight of the treated plants was compared. Our results in VI. are shown in the table.

VI. spreadsheet

Herbicide antidote cultural plant green Weight % of control The chemical name of the active substance Dose (Kg / ha) Serial number of compound Dose spraying (Kg / ha) dressing (Kg / q) spraying dressing 2-Chloro-2'-methyl-6'-ethyl-N- (ethoxymethyl) acetanilide + N- (3-chloro-4-bromophenyl) -N'-methyl-N '-methoxyurea 4.0 + 1.5 - - - maize 52 52 4.0 + 1.5 1 1 1.0 0.5 maize 102 99 2-Chloro-2'-methyl-6'-ethyl-N- (ethoxymethyl) acetanilide + N- (4-bromophenyl) -N'-methyl-N '-methoxyurea 4.0 + 1.0 - - - maize 48 48 4.0 + 1.0 7 7 1.0 0.5 maize 98 100 2-Chloro-2'-methyl-6'-ethyl-N- (ethoxymethyl) acetanilide + N- (3-chlorophenyl) -N'-methyl-N '-methoxyurea 4.0 + 1.25 - - - maize 47 47 4.0 + 1.25 1 1 1.0 0.5 maize 104 102 2-chloro-2 ', 6'-diethyl-N- (methoxymethyl) - acetanilide + N- (benzothiazol-2-yl) - -N-methyl-urea 4.0 +0.75 - - - sunflower 32 32 4.0 +0.75 1 1 1.0 0.5 sunflower 97 105 4.0 +0.75 2 2 1.0 0.5 sunflower 95 93 4.0 +0.75 3 3 1.0 0.5 sunflower 92 94 2-Chloro-2 ', 6'-diethyl-N- (methoxymethyl) -acetamide + N- (4-trifluoromethyl-phenyl) -N', N '-dimethyl-urea 5.0 + 1.0 - - - maize 43 43 5.0 + 1.0 1 1 1.0 0.5 sunflower 107 105 5.0 + 1.0 4 4 1.0 0.5 sunflower 95 93 5.0 + 1.0 5 5 1.0 0.5 sunflower 86 92

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VI. Continue Table

Herbicide antidote cultural Plant green Weight % of control The chemical name of the active substance Dose (Kg / ha) Serial number of compound Dose spraying I dressing (kg / ha) (Kg / q) spraying dressing 2-Chloro-2'-ethyl-6'-methyl-N- (1-methyl-2-methoxy-ethyl) -acetanyl id + N- (3,4-dichlorophenyl) -N'-butylurea 8.0 + 1.5 - - - maize 55 55 8.0 + 1.5 1 1 1.0 0.5 maize 104 101 8.0 + 1.5 6 1.0 0.5 maize 78 81 8.0 + 1.5 7 1.0 0.5 maize 102 105 2-chloro-2 ', 6'-diethyl-N- (l, 3-dioxolane -2-ylmethyl) acetanilide + N- (4-chloro- phenyl) -N '- (l-methyl-2-propynyl) -N'- methylurea 4.0 + 1.0 - - - maize 48 48 4.0 + 1.0 8 8 1.0 0.5 maize 96 93 4.0 + 1.0 9 9 1.0 0.5 maize 92 95 2-Chloro-2 ', 6'-diethyl-N- (ethoxycarbonylmethyl) -acetanyl id + N- (3-chloro-4-methyl-phenyl) -N', N-dimethylurea 5.0 + 1.5 - - - maize 53 53 5.0 + 1.5 7 7 1.0 0.5 maize 103 105 5.0 + 1.5 10 10 1.0 0.5 kulorica 86 92 5.0 +1.5 11 11 • 1.0 0.5 maize 91 94 2-Chloro-2 ', 6'-dimethyl-N- (methoxymethyl) -acetanilide + N -cyclooctyl-N', N'-dimethylurea 5.0 +2.0 - - - maize 41 41 5.0 +2.0 1 1 1.0 0.5 maize 102 103 5.0 +2.0 12 12 1.0 0.5 maize 81 85 5.0 +2.0 13 13 1.0 0.5 maize 85 80 2-chloro-2 ', 6'-diethyl-N- (butoxymethyl) -acetanilide + N- (3,4-dichlorophenyl) -N N '-dimethylurea 5.0 + 1.5 - - - maize 56 56 , 5.0 + 1.5 1 1 1.0 0.5 maize 108 105 5.0 + 1.5 14 14 1.0 0.5 maize 91 90 5.0 + 1.5 15 15 1.0 0.5 maize 95 92 2-chloro-2 ', 6'-dimethyl-N- (isopropoxy-me- methyl) acetanilide & N-phenyl-N ', N'-dimethyl- -urea 5.0 +2.0 - - - maize 61 61 5.0 +2.0 7 7 1.0 0.5 maize 105 103 5.0 +2.0 16 16 1.0 0.5 maize 87 90 2-chloro-2'-methyl-6'-tert-butyl-N- (butoxy -methyl) acetanilide + N- (3,4-dichloro phenyl-N-methyl-N'-methoxy-urea 5.0 +0.75 - - - maize 48 48 5.0 +0.75 1 1 1.0 0.5 maize 103 105

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VI. Continue Table

Herbicide antidote cultural Plant % Of green weight control The chemical name of the active substance Dose (Kg / ha) Serial number of compound Dose spraying (Kg / ha) dressing (Kg / q) spraying | dressing 2-chloro-2'-methyl-6'-tert-butyl-N- (butorxi methyl) -acetanilid- + N- (3,4-dichloro- 5.0 +0.75 17 17 1.0 0.5 maize 78 83 phenyl) -N'-methyl-N'-methoxy-urea 5.0 +0.75 18 18 1.0 0.5 maize 81 85 2-chloro-N-isopropyl-acetanilide + N- [3- (l, l, 2,2-tetrafluoro-ethoxy) phenyl-N ', N' 8.0 + 1.0 - - - maize 59 59 dimethyl-urea 8.0 + 1.0 1 1 1.0 0.5 maize 112 108 2-Chloro-N-isopropylacetanilide + N- [3] -1,1,2,2-tetrafluoro-ethoxyphenyl-N ', N'-dimethylurea 8.0 + 1.0 19 19 1.0 0.5 maize 92 95 2-chloro-N- (1-methyl-2-propynyl) acetanilide + + N - [(4-chlorophenoxy) phenyl] -N ', N'- 4.0 +0.75 - - - sunflower 37 37 dimethyl-urea 4.0 +0.75 1 1 1.0 0.5 sunflower 100 102 4.0 +0.75 7 7 1.0 0.5 sunflower 102 105 2-chloro-2'-methyl-6'-ethyl-N- (ethoxymethyl) acetanilide + N- (4-bromophenyl) -N '-methoxy-N' -methyl urea + 2-chloro- 0.5 + 1.0. +0.8 - - - maize 42 42 4- (ethylamino) -6- (isopropylamino) - 1,3,5-triazine 5.0 + 1.0 0.8 1 1 1.0 0.5 sunflower 112 108 2-chloro-2 ', 6'-diethyl-N- (methoxymethyl) -acetanilide + N- (3,4-dichlorophenyl) -N'-methoxy-N'-methylurea + 2-chloro- 4- 6.0 + 1.5 + 1.0 - - - maize 38 38 - (l-cyano-l-methyl-amino) -6- (ethylamino) - 1,3,5-triazine 6.0 + 1.5 + 1.0 7 7 1.0 0.5 maize 103 100 2-chloro-2'-ethyl-6'-methyl-N- (l-methyl-2-methoxyethyl) acetanilide + N- (benzothiazol-2-yl) -N, N'-dimethylurea + 2 - 6.0 + 1.0 +0.75 - - maize 46 46 chloro-4- (cyclopropylamino) -6- (iso propylamino -) - l, 3,5-triazine 6.0 + 1.0 +0.75 7 1.0 0.5 maize 104 102 2-chloro-2 ', 6'-diethyl-N- (l, 3-dioxolan-2-ylmethyl) acetanilide + N- (4-trifluoromethyl-phenyl) -N', N'-dimethyl- urea + 5.0 + 1.0 + 0.5 1 - - maize 51 51 + 2-methylthio-4,6-bis (isopropylamino) -1,3,5-triazine 5.0 + 1.0 5.0 1 1 1.0 0.5 maize 102 104 2-chloro-2 ', 6'-diethyl-N- (ethoxycarbonyl methyl) acetanilide + N- (4-isopropyl-Fe phenyl) -N ', N'-dimethyl-urea +2 5.0 + 0.5 + 1.5 - - - maize 53 53 -methyl-thio-4- (ethylamino) -6- (tert-butylamino) -1,3,5-triazine 5.0 + 0.5 + 1.5 7 7 1.0 0.5 maize 98 95

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VI. Continue Table

Herbicide antidote cultural Plant green Weight % of control The chemical name of the active substance Dose (Kg / ha) Serial number of compound Dose spraying and dressing (kg / ha) (Kg / q) spraying dressing 2-chloro-2 ', 6'-diethyl-N- (methoxymethyl) acetanilide + 2-chloro-2'-ethyl-6'-methyl-N- (l-methyl-2-methoxy-ethyl) - acetanilide + + N- (3-chloro-4-methoxyphenyl) -N, N-dimethylurea + 2-methoxy-4- (ethylamino) -6- (tert-butylamino) -1,3 5-triazine 2.5 +5.0 +0.5 + 1.0 - - - maize 45 45 2.5 +5.0 +0.5 + 1.0 1 1 1.5 0.5 maize 107 102 S-ethyl-N, N-dipropyl-thiolcarbamate + + 2-chloro-2'-methyl-6'-ethyl-N- (ethoxymethyl) -acetanilide + N- (4-bromophenyl) -N'- methoxy-N-methylurea 2.0 +4.0 + 1.0 - - - maize 38 38 2.0 +4.0 + 1.0 1 1 1.0 0.5 maize 104 103 S-ethyl N, N-diisobutyl thiolcarbamate + + 2-Chloro-2'-ethyl-6'-methyl-N- (1-methyl-2-methoxy-ethyl) -acetanilide + N- (3-chloro-4-trifluoromethyl-phenyl) -N ', N'-dimethyl-urea 6.0 + 1.0 + 1.5 - - maize 43 43 6.0 + 1.0 + 1.5 1 1 1.0 0.5 maize 101 102 S-propyl N, N-dipropylthiolcarbamate + + 2-chloro-2 ', 6' -detyl-N- (ethoxycarbonylmethyl) acetanilide + N- [4- (4-chlorophenoxy) phenyl] -N ', N'-dimethyl urea + + 2-chloro-4- (ethylamino) -6- (isopropylamino) -1,3,5-triazine 3.0 + 3.0 +0.2 + 1.5 - - - maize 47 47 3.0 +3.0 +0.2 + 1.5 7 7 1.0 0.5 maize 105 101 S-ethyl-N-cyclohexyl-N-ethyl-thiolcarbamate + + 2-chloro-2 ', 6'-dimethyl-N- (methoxymethyl) -acetanilide + N- (2-methyl-cyclohexyl) -N- (phenyl) urea + 2-methylthio-4- (l-cyano-l-methyl-ethylamino) -6- (ethylamino) -1,3,5-triazine 0.5 +6.0 +0.1 +2.0 - - maize 51 51 0.5 +6.0 +0.1 +2.0 1 1 1.0 0.5 maize 102 100 S- (4-chlorobenzyl) -N, N-diethyl thiolcarbamate + 2-chloro-N-isopropyl-acetanilide + N- (3,4-dichlorophenyl) -N, N-dimethylurea 9.0 +0.5 + 1.5 - - 0.5 maize 45 45 9.0 +0.5 +1.5 1 1 1.0 maize 103 104 S-ethyl N, N-hexamethylene thiolcarbamate + + 2-chloro-N-isopropylacetanilide + + N-phenyl-N ', N'-dimethylurea 0.5 +9.5 +0.2 - - - maize 61 61 0.5 +9.5 +0.2 1 1 1.0 0.5 maize 110 107

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Herbicide antidote cultural Plant green Weight % of control The chemical name of the active substance Dose (Kg / ha) Serial number of compound Dose spraying (Kg / ha) dressing (Kg / q) spraying dressing S- (4-methoxybenzyl) -N, N-diethylthiolcarbamate + 2-chloro-N-isopropylacetanilide-N- (1,2,3-thiadiazol-5-yl) -N'-phenyl urea + 2-methylthio-4- (isopropylamino) -6- (methylamino) -l, 3,5-triazine 3.0 +6.0 +0.75 +0.5 - - - maize 61 61 3.0 +6.0 +0.75 +0.5 7 7 1.0 0.5 maize 100 102 S- (2,3,3-trichloro-allyl) -N, N-diisopropyl-thiolcarbamate + 2-chloro-N- (l-methyl-2-propynyl) acetanilide + N- (3-chloro-4-methyl -phenyl) -N ', N' -dimethylurea + + 2-azido-4-isopropyl-6-methylthio-1,3,5-triazine 3.0 + 3.0 +0.5 +0.5 - - - maize 58 58 3.0 + 3.0 +0.5 +0.5 1 1 1.0 0.5 maize 98 96

Example C)

Field Biological Experiment I.

Based on the results of the greenhouse, a field experiment was carried out according to the invention of formula (I).

compounds of the chloroacetanilide type and the urea type and the triazine type and thiolcarbamate type in herbicide under field conditions. For the experiments, the following formulations were prepared (by appropriate dry or wet milling). 35 A) A wettable powder formulation 40 2-Chloro-2'-methyl-6'-ethyl-N- (ethoxymethyl) acetanil id N- (4-bromophenyl) -N'-methoxy-N'-methyl 40% by weight -urea 8% by weight N-dichloroacetyl-1-oxa-4-azaspiro (4,5) decane (Compound No. 1) 7% by weight 45 emulsifier: Na-oleylmethyl tauride dispersant: sodium lignin 5% by weight sulfonate 3% by weight colloidal synthetic silica 15% by weight 50 kaolin 22% by weight 100% by weight B) A wettable powder formulation 55 2-chloro-2'-methyl-6'-ethyl-N- (ethoxymethyl) - acetanilide 40% by weight N- (4-bromophenyl) -N'-methoxy-N'-methyl -urea 8% by weight emulsifier: Na-oleylmethyl tauride dispersant: sodium lignin 5% by weight 60 sulfonate 3% by weight colloidal synthetic silica 18% by weight kaolin 26% by weight 100% by weight 65

Shoot

C) Aqueous colloidal suspension 2-chloro-2'-methyl-6'-ethyl-N- (ethoxymethyl) - acetanilide N- (3-chloro-4-bromophenyl) -N-methoxy-N methylurea ^O / _o by weight 40% weight 4 2-chloro-4- (ethylamino) -6- (isopropylamino) -1,3,5-triazine 6% by weight N- (dichloroacetyl) -1-oxa-4-azaspiro- (4,5) decane # 1. Compound Emulsifier: Polyoxyethylene alkyl 8% by weight -Aryl ether (Atlox 1690, Atlas Chemie) dispersant: sodium lignin 4% by weight sulfonate 3% by weight protective colloid: lecithin 1% by weight colloidal synthetic silica 3% by weight WATER 31% by weight 100% by weight D) Aqueous colloidal suspension 2-chloro-2'-methyl-6'-ethyl-N- (ethoxymethyl) - acetanilide 40 weight ° / " N- (3-chloro-4-bromophenyl) -N'-methoxy-N-methylurea 2-chloro-4-ethylamino-6- (isopropylamino) - 4% by weight 1,3,5-triazine emulsifier: polyoxyethylene alkyl 6% by weight aryl ether 4 weights / 'oh dispersant: sodium lignin sulfonate 3% by weight protective colloid: lecithin 1% by weight colloidal synthetic silica 5% by weight WATER 37 dumbbells 100% by weight E) A wettable powder formulation 2-chloro-2 ', 6'-diethyl-N- (methoxymethyl) - acetanilide 20% by weight S-propyl N, N-dipropylthiolcarbamate 20% by weight N-phenyl-N ', N' -dimethylurea 3% by weight

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2-Methyl-4- (1-cyano-1-methyl-ethyl) amino) -6- (ethylamino) -l, 3,5-triazine N- (dichloroacetyl) -l-thia-4-azaspiro 5 weight ⁰ /) - (4,5) Dean no. compound 4 weight /., emulsifier: Na-oleylmethyl tauride dispersant: sodium lignin 5% by weight sulfonate 3% by weight colloidal synthetic silica 17 wt% kaolin F) A wettable powder formulation 2-chloro-2 ', 6'-diethyl-N- (methoxymethyl) - 23% by weight 100% by weight acetanilide 20% by weight S-propyl N, N-dipropylthiolcarbamate 20 weight /), N-phenyl-N ', N'-dimethylurea 2- (methylthio) -4- (l-cyano-l-methylethyl 3% by weight amino) -6-ethylamino-l, 3,5-triazine 5% by weight emulsifier: Na-oleylmethyl tauride dispersant: sodium lignin 5% by weight sulfonate 3% by weight colloidal synthetic silica 17% by weight kaolin 27% by weight G) A wettable powder formulation 100% by weight S-ethyl N, N-diisobutyl thiolcarbamate N- (3,4-dichlorophenyl) -N ', N' -dimethyl- 30% by weight urea 2-chloro-4- (ethylamino) -6- (isopropyl 2% by weight amino) -l, 3,5-triazine N-dichloroacetyl-l-oxa-4- 3 weight'X -azaspiro (4,5) Dean No. 1; Compound Emulsifier: Na-oleylmethyl 3 weight), -taurid dispersant: sodium lignin 5% by weight sulfonate 3% by weight colloidal synthetic silica 20 weight /), kaolin H) A wettable powder formulation 34% by weight 100% by weight S-ethyl N, N-diisobutyl thiolcarbamate N- (3,4-dichlorophenyl) -N ', N'-dimethyl- 30% by weight -urea 2-chloro-4- (ethylamino) -6- (isopropyl 2% by weight amino) -l, 3,5-triazine 3% by weight emulsifier: Na-oleylmethyl tauride dispersant: sodium lignin 5% by weight sulfonate 3% by weight colloidal synthetic silica 20 weight /), kaolin I) Granule preparation 37% by weight 100% by weight S-ethyl-N, N-dipropylthiolcarbamate 2-chloro-2 ', 6'-diethyl-N- (butoxymethyl) - 0.8% by weight acetanilid 2-chloro-4- (ethylamino) -6- (isopropyl- 0.8% by weight amino) -l, 3,5-triazine 0.5% by weight antidote: no. compound 0.4% by weight attapulgite 97.5% by weight / ₀ 100% by weight

J) Granulate preparation (herbicidal active substances)

S-ethyl N, N-dipropylthiolcarbamate 2-chloro-2 ', 6'-diethyl-N- (butoxymethyl) - 0.8 weight ⁰ /) acetanilide 2-chloro-4- (ethylamino) -6- (isopropyl 0.8 weight% amino) -l, 3,5-triazine 0.5 weight/) attapulgite 97.5 weight% K) Wettable powder formulation 100 weight% 2-chloro-N-isopropyl-acetanilide N- (3-chloro-4-bromophenyl) -N'- 85 weight% methyl-N'-methoxy-urea 4.25% by weight antidote: no. Compound Emulsifier: Na-oleylmethyl 0.1 weight% -taurid dispersant: sodium lignin 4 weight% sulfonate 3 weight% kaolin 3.65 weight% L) Wettable Powder Formulation (Herbicidal) 100 weight% 2-chloro-N-isopropylacetanilide N- (3-chloro-4-bromophenyl) -N-methyl 85 weight% N'-methoxyurea emulsifier: Na-oleylmethyl- 4.25 weight /) -taurid 4 weight% dispersant: sodium lignin y sulfonate 3 weight%

kaolin 3.75% by weight

UHW weight%

M) Oily colloidal suspension formulation

S-propyl N, N-dipropylthiolcarbamate 2 k1ór-2'-methyl-6'-ethyl-N- (ethoxy 10% by weight methyl) acetanilide 2-chloro-4,6-bis (ethylamino) -l, 2,5- 5% by weight triazine 3% by weight antidote: no. Compound Emulsifier: Na-oleylmethyl 9% by weight -taurid 7 weights /) paraffin 66 weight /) 100 weight /) N) Oily suspension formulation (herbicidal agents) S-propyl N, N-dipropylthiolcarbamate 2-chloro-2'-methyl-6'-ethyl-N- (ethoxymethyl) - 10 weight / ·) acetanilide 2-chloro-4,6-bis (ethylamino) -1,2,5- 5% by weight triazine emulsifier: Na-oleylmethyl 3% by weight -taurid 7% by weight paraffin 75% by weight

100% by weight

The size of the experimental plots was 20 m ² . To demonstrate the protective effect, formulations of the above formulations were sprayed at approximately twice the dose used in maize herbicide. For comparative control, formulations "B", "D", "F", "H", "J", "K" and "N" were prepared without the active ingredient but with the same herbicidal composition. The formulations were 3001 / ha17

-17181621 was sprayed onto the soil, and granules I and J were evenly dispersed without the addition of water and then worked with a rotary hoe 5 cm deep into the soil. The treated areas were sown with SC 3269 maize. The effect of the formulations was evaluated 18 weeks after sowing. Both the harmful effect on maize and the herbicidal effect were studied. The assessment was based on the internationally accepted EWRC scale based on visual assessment.

Each value has the following meaning:

EWRC value- song Phytotoxic effects seen on crop plants Herbicide ° / o general impression First There are no 100 excellent Second very slightly 98 very good Third 4th slight effect strong, but probably transient damage, loss of crop 95 good and unlikely 90 satisfying 5th uncertain phenomena 82 in question 6th detectable damage 70 unsatisfactory OO severe damage very strong damage- 55 bad Das 30 very bad 9th total destruction 0 használha- insoluble

The experiments were performed in 4 replicates, the EWRC values given are the weighted averages of the 4 replicates.

It is clear from the table above that the herbicidal activity of formulations containing the active ingredient (A, C, E, G, I, K and M) is practically the same as that of herbicides alone. preparations ("B", "D", "F", "H", "I", "L" and "N"). However, while herbicide-only formulations significantly damage corn, combinations containing the antidote drug do not harm the maize at all.

Example D)

Field experiment II.

In order to investigate the effect of the compounds represented by the general formula (I) according to the invention as an antidote, we designed an experiment in which the independently formulated antidote of formula (I) was sprayed separately and separately (II), (IV), ( V) and (VI) herbicides. Separately in the form of 25 mixtures. In our experiment, we investigated whether the antidote and the herbicides were sprayed separately on the soil to ensure the protective effect of the antidote.

As an antidote in each of the experiments, no. Compound N-dichloroacetyl-1-oxa-4-azaspiro- (4,5) -decane was included as a powder formulation containing 70% by weight of active ingredient.

VII. spreadsheet

Product sign Dose (Kg / ha) weeds phytotoxicity corn Echinochloa crus-galli Digitaria sanguinalis Setaria viridis Chenopodium Aldura Amaranthus retroflexus THE 10 2 2 1 1 2 1 B 10 2 2 1 2 3 6.5 C 10 1 1 1 2 2 1 D 10 1 2 1 2 2 6.5 E 15 1 1 1 2 3 1 F 15 1 1 1 2 3 6 G 20 2 2 1 2 3 1 H 20 2 2 1 2 4 6.5 I 200 1.5 2 2 2.5 4 1 J 200 1.5 2 2 3 4 6 K 10 1 2. 2.5 2 3 1.5 L 10 1 2.5 2 2 3 5.5 M 40 1 2 2 2.5 3 1 N 40 1 2.5 2 2 3 6

For herbicidal combination, formulations "B", "D", "F" and "H" in the previous example were used.

The size of the experimental fields was 20 m ² . Our experiments were carried out as follows.

The soil was first treated with an antidote. For this purpose, an amount of the wettable powder composition of the exemplary 70% w / w antidotate active compound was sprayed onto the experimental parcel after dilution with 400 l / ha water and worked with a rotary hoe at a depth of 5 cm. (1.44 kg / ha 70% active ingredient. The formulation corresponds to 1 kg / ha active ingredient). The experimental plot was then seeded with SC 3269 maize seed. One week after sowing, an amount of the given her60 bicid combination was sprayed onto the experimental parcel after dilution with 300 L / ha water (preemergent treatment).

Evaluation of the effect of the preparations after sowing

We were done 18 weeks later. We tested both on maize

-18181621 had a harmful effect and a herbicidal effect. The assessment was based on the internationally accepted EWRC scale based on visual assessment.

The experiments were performed in 4 replicates, the EWRC values given are the weighted averages of the 4 replicates.

As a control, treatment with herbicidal combinations was carried out as described above, 1 week after sowing, but the soil was not treated with the exemplary antidote formulation prior to sowing.

VIII. spreadsheet

preparation Dose (Kg / ha) weeds Fitotoxiditás corn Echinochloa crus-galli Digitaria sanguinalis Setaria ✓iridis Chenopodium album Amaranthus retroflexus antidote B 1.44 10 2 2 1 1 2 1 B , 10 2 2 1 1 3 6.5 antidote D 1.44 10 1 1 1 2 2 1 D 10 I 2 1 2 2 6.5 antidote F 1.44 15 2 1 1 2 3 1 F 15 1 1 1 2 3 6.5 antidote H 1.44 20 3 2 2 1 4 1 H 20 2 2 2 2 4 6.5

It is clear from the table above that anti-dotamous treatment did not substantially reduce the herbicidal activity of the multi-herbicides, but completely eliminated their phytotoxic effect on maize. According to our results, the antidoticidal composition according to the invention can effectively eliminate the harmful phytotoxic effect of the applied herbicides on maize even if the herbicidal and antidoticidal compositions are applied separately to the soil at different times.

Example E)

Biological impact assessment in a greenhouse (spraying)

The phytotoxic effects of various compositions of thiolcarbamate-type herbicides of formula II and chloroacetanilide herbicides of formula IV and triazine herbicides of formula V on crop plants are counteracted by the active compounds of the present invention 50 greenhouse studies were performed. The test herbicides were available in the form of a formulation by the manufacturer. The amounts needed for spraying were measured so that the doses calculated for the active ingredient in the attached table were sprayed. (For example, for the herbicide of 55 S-ethyl-N, N-dipropylthiolcarbamate, Eptam 6E emulsifiable formulation containing 76.9% w / v, 9.75 kg / ha of active substance corresponds to 12.68 kg / ha of Eptam 6E formulation 5 kg / ha of Acetochlor 50 EC emulsifiable preparation containing 50% by weight of active ingredient 2-chloro-2'-methyl-6'-ethyl-N-ethoxy-60-methylacetanilide. 1.0 kg from the Hungazin PK 50 WP wettable powder formulation containing 2% of the active ingredient 2-chloro-4- (isopropylamino) -6- (ethylamino) -1,3,5-triazine containing 50% w / w of the active ingredient / ha of active ingredient corresponds to 2 kg / ha of formulation.)

The active compounds of the formula I according to the invention were used as a wettable powder formulation containing 70% by weight of the active ingredient and as an emulsifiable formulation containing 50% by weight of the active ingredient as described in the formulation examples. Doses were selected to correspond to the active ingredient dose as given in the appended table (e.g., 1 kg / ha of the 70 wt / wettable powder formulation corresponds to 1.44 kg / ha of formulation).

The experiments were carried out in 15 cm diameter pots, 5 replicates per experiment. The pots were filled with sandy loam soil up to 5 cm from the top of the tile, then 10 seeds of maize and sorghum seeds of varieties 32SC were placed on top of the soil. The seeds were then covered with soil treated or untreated according to the experiment, 5 cm thick. The herbicidal compositions converted to soil of a given surface area were diluted with water equivalent to 400 liters / ha of water and then sprayed with an aqueous emulsion of the given herbicide in a small concrete mixer. The treated soil was immediately covered with seeds in the pots.

The method of combining herbicide antidotes was the same as herbicide treatment, except that the amount of herbicides calculated on the soil surface at 400 l / ha water was diluted and sprayed. while stirring to the soil. Seeds prepared as described above were immediately covered with the treated soil in a 5 cm thick layer. For quantitative evaluation, untreated controls were set up in the same manner as the treated experiments with 5 untreated cultures per crop. For the experiment

-19181621 prepared pots were then kept in a greenhouse, watered as needed. Evaluation was carried out 4 weeks after sowing. For evaluation, the plants were cut above the soil and weighed. Results are expressed as the mean of 6 replicates. The weight of the untreated control green plant was taken as 100% and compared to the weight of the treated plants. Our results are in Section IX. are shown in the table.

Example F)

Biological experiment in a greenhouse (dressing)

Greenhouse experiments were conducted to investigate the extent to which the compounds of formula (I), the thiolcarbamate-type herbicides of formula (II) and the chloroacetanilide-type herbicides of formula (IV) and the triazine-type herbicides of formula (V) the crop-damaging effects of various mixtures of herbicides by applying a compound of formula (I) to the crop seed and applying the seed to the soil treated with the herbicidal mixture. The experimental conditions and experimental setups were the same as for greenhouse spraying experiments, except that the soil was treated with herbicide only. The seed was treated with a wettable powder composition containing 70% by weight of the active ingredient or 50% by weight of an emulsifiable composition of the compounds of formula I according to the invention at the dose indicated in the attached table.

For seeding, 100 g of seed was mixed in a 1-liter flask with the following seed dressing:

Dose of 0.5 kg / q active ingredient 0.5 g of active ingredient per 100 g of seed. On this basis, 0.715 g of a wettable powder formulation containing 70% by weight of the active ingredient

1.5 ml of distilled water were mixed and the seeds were shaken in the flask until the wall was clear. The seeds so treated were then placed in pots prepared as described above. As a comparative study, untreated controls were set for each crop at 5 replicates per crop. The prepared pots were kept in a greenhouse, watered as needed.

seven weeks later, the mature plants were cut above the ground and weighed. The results are given in duplicate. The weight of the untreated control green plant was taken as 100% and compared to the weight of the treated plants. Our results are in Section IX. are shown in the table.

IX. spreadsheet

Herbicide antidote cultivated Green weight in% of control The chemical name of the active substance Dose (Kg / ha) Serial number of compound Dose spraying dressing spraying (Kg / ha) dressing (Kg / q) S-ethyl-N, N-dipropyl-thiolcarbamate + 2-chloro-2'-methyl-6'-ethyl-N- (ethoxymethyl) -acetane 1d + 2-chloro-4- (ethyl-1-amino) ) -6- (isopropyl-1-amino) -1,3,5-triazine 5.0 + 2.5 + 1.0 - - maize 45 45 5.0 + 2.5 + 1.0 1 1 1.0 0.5 maize 108 106 5.0 + 2.5 + 1.0 7 7 1.0 0.5 maize 104 107 S-ethyl N, N-dipropyl thiolcarbamate + 2-chloro 2'-methyl-6'-ethyl-N- (ethoxymethyl) acetamido anilide + 2-chloro-4- (ethylamino) -6- (isopropyl- amino) -l, 3,5-triazine + 2-chloro-4- (l-cyano l-methyl-ethylamino) -6-ethylamino-l, 3,5- triazine 5.0 +2.5 +0.5 +0.75 - - - maize 47 47 5.0 +2.5 +0.5 +0.75 1 1 1.0 0.5 maize 105 102 5.0 +2.5 +0.5 +0.75 7 7 1.0 0.5 maize 103 104 S-propyl-Ν, Ν-dipropylthiolcarbamate + + 2-chloro-2 ', 6'-diethyl-N- (methoxymethyl) acetanilide + 2-chloro-4- (1-cyano-1-methyl-ethyl) amino) -6- (ethylamino) -l, 3,5-triazine + 2-methylthio-4- (ethylamino) -6- (tert-butylamino) -l, 3,5- triazine 5.0 +2.5 +0.75 +0.5 - - - maize 56 56

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Herbicide antidote cultural Plant green Weight % of control The chemical name of the active substance Dose (Kg / ha) Serial number of compound Dose spraying dressing spraying (Kg / ha) dressing (Kg / q) S-propyl N, N-dipropyl thiolcarbamate + + 2-chloro-2 ', 6'-diethyl-N- (methoxymethyl) acetanilide + 2-chloro-4- (1-cyano-1-methylethylamino) -6- (ethylamino) ) -l, 3,5-triazine + 2-methyl) thio-4- (ethylamino) -6- (tert-butylamino) -l, 3,5-triazine 5.0 + 2.5 +0.75 +0.5 1 1 1.0 0.5 maize 110 102 S-ethyl N, N-diisobutyl thiolcarbamate + 2-chloro -2'-ethyl-6'-methyl-N- (l-methyl-2-methoxy- ethyl) acetanilide + 2-chloro-4- (ethylamino) - -6- (isopropylamino) -l, 3,5-triazin-2 + Cl 5.0 + 5.0 + 0.5 + 0.5 - - - maize 54 54 -4- (cyclopropylamino) -6- (isopropylamino) 1,3,5-triazine 5.0 + 5.0 +0.5 +0.5 1 1 1.0 0.5 maize 107 103 S-ethyl-N, N-hexamethylene thiolcarbamate + 2-chloro-2 ', 6'-diethyl-N- (ethoxycarbonyl-methyl) acetanilide + 2-chloro-4- (ethylamino) - (isopropyl amino) -l, 3,5-triazine + 2-methylthio-4- (ethylamino) -6- (tert-butylamino) -1,3,5-triazine 3.0 + 3.0 +0.5 +0.5 - - - maize 50 50 S-ethyl N, N-hexamethylene tiolkarbaniát- +2 chloro-2 ', 6'-diethyl-N- (ethoxycarbonyl-methyl) - + acetanilide 2-chloro-4- (ethylamino) -6- (iso- propylamino) -l, 3,5-triazine & methylthio-4- 3.0 + 3.0 +0.5 +0.5 1 1.0 0.5 maize 102 105 - (ethylamino) -6-fterc-butylamino) -l, 3,5- triazine 3.0 +3.0 +0.5 +0.5 7 7 1.0 0.5 maize 98 102 S-ethyl-N-cyclohexyl-N-ethyl thiolcarbamate + 2-chloro-2 ', 6'-diethyl-N- (butoxymethyl) -acetani1id + 2-chloro-4,6-bis (ethylamino) -l, 3,5- 4.0 +3.0 + 1.0 - - - maize 57 57 triazine 4.0 + 3.0 + 1.0 1 1 1.0 0.5 maize 102 100 4.0 + 3.0 + 1.0 7 7 1.0 0.5 maize 100 103 S- (4-chlorobenzyl) -N, N-diethyl-thiolcarbamate + 2 chloro-N- (l-methyl-2-propynyl) acetanilide +2 chloro-4- [l-cyano-l-methyl (ethylamino)] - -6-ethylamino-l, 3,5-triazin-2-methoxy-+ 5.0 + 3.0 +0.75 -! 0.5 - - - maize 58 58 4- (ethylamino) -6- (tert-butylamino) - 1,3,5-triazine 5.0 + 3.0 +0.75 +0.5 1 1 1.0 0.5 maize 97 100 5.0 + 3.0 +0.75 +0.5 7 7 1.0 0.5 maize 102 105 S-ethyl N, N-diisobutyl-tioIkarbamát + 2-chloro-N-isopropyl-acetanilide + 2-methylthio-4- 4.0 + 5.0 sorghum 37 37

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Herbicide antidote cultural Plant Zöídsúly % of control The chemical name of the active substance Dose (Kg / ha) Λ compound serial number Dose spraying dressing spraying, dressing (Kg / ha) (Kg / q) - (ethylamino) -6- (tert-butylamino) - -1,3,5-thiazine + 2-chloro-4- (1-cyano-1-methyl-1- ethylamino) -6- (ethylamino) -l, 3,5-triazine +0.5 +0.5 - 4.0 + 5.0 +0.5 +0.5 1 1 1.0 0.5 sorghum 98 102 4.0 +5.0 +0.5 +0.5 7 7 1.0 0.5 sorghum 103 100 S-ethyl-N, N-dipropylthiolcarbamate + 2-chloro-4-methyl-amino) -6- (isopropylamino) - 9.75 + 1.0 - - - maize 45 . 45 1,3,5-triazine 9.75 + 1.0 1 1 1.0 0.5 maize 108 106 S-ethyl-N, N-dipropyl thiolcarbamate + 2-methyl- thio-4- (ethylamino) -6- (tert-butylamino) - 9.75 +0.75 - - - maize 47 47 1,3,5-triazine 9.75 +0.75 2 2 1.0 0.5 maize 98 100 S-ethyl-N, N-dipropyl-thiolcarbamate + 2-chloro-4- (1-cyano-1-methyl-ethylamino) -6- (ethyl- 9.75 ~ h - - - maize 49 49 amino) -l, 3,5-triazine 9.75 + 1.5 3 3 1.0 0.5 maize 94 89 S-propyl-N, N-dipropyl-thiolcarbamate + 2-chloro-4- (cyclopropyl) -amino) -6- (isopropyl- 6.0 + 1.0 - - - maize 57 57 amino) -l, 3,5-triazine 6.0 + 1.0 1 1 1.0 0.5 maize 101 103 6.0 + 1.0 4 4 1.0 0.5 maize 96 93 S-ethyl N, N-diisobutyl thiolcarbamate + 2 methylthio-4- (l-cyano-l-methyl-ethylamino) - 7.0 +0.8 - - - maize 62 62 6- (ethylamino) -l, 3,5-triazine 7.0 +0.8 1 1 1.0 0.5 maize 103 105 7.0 +0.8 5 5 1.0 0.5 maize 92 95 S-ethyl N, N-diisobutyl thiolcarbamate + 2-chloro 4,6-bis (ethylamino) -l, 3,5-triazine 8.0 + 1.0 - - - maize 67 67 8.0 + 1.0 1 1 1.0 0.5 maize 104 100 8.0 +1.0 6 6 1.0 0.5 maize 87 89 S-ethyl-N-cyclohexyl-N-ethyl thiolcarbamate + 2-chloro-4,6-bis (isopropylamino) -l, 3,5- 8.0 +0.8 - - - maize 57 57 triazine 8.0 +0.8 1 1 1.0 0.5 maize 97 102 8.0 4 0.8 7 7 1.0 0.5 maize 99 101

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Herbicide antidote cultural Plant Zöldsűly The chemical name of the active substance Dose (Kg / ha) Serial number of compound But spraying (Kg / ha) zis dressing (Kg / q) spraying dressing S-ethyl-N-cyclohexyl-N-ethyl-2- & tioIkarbamát -metiItio-4,6-bis (isopropylamino) - 1,3,5-triazine 8.0 + 1.0 - - - maize 60 60 8.0 + 1.0 1 1 1.0 0.5 maize 104 105 8.0 + 1.0 8 8 1.0 0.5 maize 96 98 S-ethyl-N-cyclohexyl-N-ethyl thiolcarbamate + 2-methoxy-4- (ethylamino) -6- (tert-butylamino) -1,3,5-triazine 3.0 +0.25 - - - sorghum 42 42 3.0 +0.25 1 1 1.0 0.5 sorghum 98 93 3.0 +0.25 9 9 1.0 0.5 sorghum 92 87 S- (4-kIórbenzil) -N, N-diethyl-thiolcarbamate + 2-methoxy-4,6-bis (isopropylamino) -l, 3,5-triazine 2.0 +0.8 - - - sorghum 31 31 2.0 +0.8 1 1 1.0 0.5 sorghum 96 98 2.0 +0.8 10 10 1.0 0.5 sorghum 86 83 S- (4-chlorobenzyl) -N, N-diethylthio-carbamate + 2-methylthio-4- (ethylamino) -6- (isopropylamino) -1,3,5-triazine 10.0 + 1.0 - - - maize 58 58 10.0 + 1.0 1 1 1.0 0.5 maize 101 104 10.0 + 1.0 11 11 1.0 0.5 maize 93 95 S-ethyl N, N-hexamethylene thiolcarbamate + 2-azido-4- (methylthio) -6- (isopropylamino) -1,3,5-triazine 6.0 +0.8 ί í 1 - maize 45 45 6.0 +0.8 1 1 1.0 1 0.5 maize 108 106 6.0 +0.8 12 · 1.0 12 0.5 maize 87 85 S-ethyl-N, N-hexamethylene thiolcarbamate + 2 methylthio-4- (methylamino) -6- (isopropyl amino) -l, 3,5-traizin 2.0 +0.3 - - - sorghum 23 23 2.0 +0.3 1 1.0 1 0.5 sorghum 95 98 2.0 +0.3 13 1.0 ¹³ 0.5 sorghum 90 92 2.0 +0.3 14 1.0 14 0.5 sorghum 87 83 S- (4-methoxybenzyl) -N, N-diethyl-tiolkloarbamát + 2- (methylthio) -4- (isopropylamino) -6- (3-methoxy-propylamino) -1,3,5 triazine 6.0 + 1.0 - '- - maize 55 55 6.0 + 1.0 1 1.0 0.5 maize 97 100 6.0 + 1.0 15 15 1.0 0.5 maize 95 97 6.0 + 1.0 16 16 1.0 0.5 maize 92 95

-23181621

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Weeds are condoms antidote cultural Plant green Weight % of control The chemical name of the active substance Dose (Kg / ha) Serial number of compound Dose spraying dressing spraying (Kg / ha) dressing (Kg / q) S- (4-methoxybenzyl) -N, N-diethylthiolcarbamate + 2-chloro-4- (isopropylamino) -6- (3-methoxypropylamino) -1,3,5-triazine 6.0 + 1.0 - - - maize 58 58 6.0 + 1.0 1 1.0 0.5 maize 102 105 6.0 + 1.0 17 17 1.0 0.5 maize 95 91 S- (2,3-dichlorallyl) -N, N-diisopropylthiolcarbamate 4 2-chloro-4- (diethylamino) -6- (isopropylamino) -1,3,5-triazine 6.0 +0.8 - - - maize 68 68 6.0 +0.8 1 1 1.0 0.5 maize 107 1Í0 6.0 +0.8 18 18 1.0 0.5 maize 94 95 S- (2,3,3-trichlorallyl) -N, N-diisopropylthiolcarbamate 4- 2- (ethylthio) -4,6-bis (isopropylamino) -1,3,5-triazine 6.0 +0.75 - - - maize 62 62 6.0 +0.75 1 1 1.0 0.5 maize 107 105 6.0 +0.75 19 19 1.0 0.5 maize 87 86 S-ethyl-N, N-dipropylthiolcarbamate + 2-chloro-4- (ethylamino) -6- (isopropylamino) -1,3,5-triazine + 2-chloro-4- (1-cyano) -1-methylethylamino) -6- (ethylamino) -1,3,5-triazine 9.75 +0.6 +0.6 - - - maize 42 42 9.75 +0.6 +0.6 1 1 1.0 0.5 maize 104 102 S-ethyl-N, N-dipropylthiolcarbamate + S-propyl-N, N-dipropylthiolcarbamate + 2- (methylthio) -4- (ethylamino) -6- (tert-butylamino) - 1,3,5-triazine 4- 2-chloro-4- (cyclopropylamino) -6- (isopropylamino) -1,3,5-triazine 5.0 + 3.0 +0.4 +0.4 - - - maize 48 48 5.0 + 3.0 +0.4 +0.4 1 1.0 0.5 maize 107 108 2-Chloro-2'-methyl-6'-ethyl-N- (ethoxymethyl) acetanilide 4- 2-chloro-4- (ethylamino) -6- (isopropylamino) -1,3,5 triazine 5.0 + 1.0 - - - maize 62 62 5.0 + 1.0 1 1 1.0 0.5 maize 112 110 2-chloro-2'-methyl-6'-ethyl-N- (ethoxymethyl) - + acetanilide 2-chloro-4- (l-cyano-l-methyl- ethylamino) -6- (ethylamino) -l, 3,5-triazine 5.0 + 1.5 - - - maize 60 60 5.0 + 1.5 1 1 1.0 0.5 maize 108 103 5.0 + 1.5 2 2 1.0 0.5 maize 101 98 2-chloro-2 ', 6'-diethyl-N- (methoxymethyl) - + acetanilide 2-chloro-4,6-bis (ethylamino) - 1,3,5-triazine 5.0 + 1.0 - - - maize 67 67 5.0 + 1.0 1 1 1.0 0.5 maize 108 105 5.0 + 1.0 3 3 1.0 0.5 maize 95 97

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Herbicide antidote cultural Plant green Weight n VrxntΓζ ~ ι11 ° / _άΗ · ιτ » The chemical name of the active substance Dose (Kg / ha) . . 1 ^Dt A of water! serial number spraying 1 (kg / ha) ZLS dressing (Kg / q) spraying dressing 2-chloro-2,6-diethyl-N- (methoxymethyl) acetanilide + 2- (methyl-lio) -4- (ethylamino) -6- (tert-butylamino) -1,3, 5-triazine 5.0 41.0 - - - sorghum 35 35 5.0 + 1.0 1 1 1.0 0.5 sorghum 98 100 5.0 + 1.0 4 4 1.0 0.5 sorghum 92 90 2-chloro-2'-ethyl-6'-methyl-N- (l-methyl-2- - (l-cyano-l-methyl-ethylamino) -6- (ethyl- amino) -l, 3,5-triazine 10.0 + 1.5 - - - maize 45 45 10.0 + 1.5 1 1 1.0 0.5 maize 104 104 10.0 + 1.5 1.0 0,5 ' maize 86 85 2-chloro-2'-ethyl-6'-methyl-N- (l-methyl-2- methoxyethyl) acetanilide + 2- (methylthio) - 4- (l-cyano-l-methyl-ethyl-amino) -6- (Ethyl amino) -l, 3,5-triazine 7.0 +0.8 - - - sorghum 41 41 7.0 +0.8 1 1 1.0 0.5 sorghum 98 97 7.0 +0.8 6 6 1.0 0.5 sorghum 87 85 2-Chloro-2'-ethyl-6'-methyl-N- (1-methyl-2-methoxy-ethyl) -acetanilide 4 2-chloro-4-methylamino-6-isopropylamino-1,3,5 triazine 10.0 +2.0 - - - maize 40 40 10.0 +2.0 1 1 1.0 0.5 maize 109 110 10.0 + 2.0 7 7 1.0 0.5 maize 105 108 2-chloro-2 ', 6'-diethyl-N- (l, 3-dioxolan-2-yl-methyl) acetanilide + 2-chloro-4- (cyclopropylamino) -6- (isopropylamino) - 1,3,5-triazine 6.0 + 1.0 - - - maize 52 52 6.0 + 1.0 1 1 1.0 0.5 maize 103 104 6.0 + 1.0 8 1.0 ⁸ , 0.5 maize 97 95 2-chloro-2 ', 6'-diethyl-N- (1,3-dioxolan-2-ylmethyl) acetanilide + 2-chloro-4,6-bis (isopropylamino) -1,3, 5-triazine 6.0 +0.8 í - maize 48 48 6.0 +0.8 11.0 i; 0.5 maize 105 100 6.0 +0.8 9 i 1.0 9 0.5 maize 93 87 2-chloro-2 ', 6'-diethyl-N- (ethoxycarbonylmethyl) acetanide + 2-methylthio) -4,6-bis (isopropylamino) -1,3,5-triazine 6.0 + 1.0 - - - maize 56 56 6.0 + 1.0 1 1.0 1 0.5 maize 110 108 6.0 + 1.0 10 ^! 1.0 ¹⁰ ! 0.5 maize 75 80 2-chloro-2 ', 6'-diethyl-N- (ethoxycarbonyl-1-methyl) -acetanilide + 2-methoxy-4- (ethylamino) -6- (tert-butylamino) -1,3, 5triazin 6.0 +0.8 -: - - maize 57 57 6.0 +0.8 1 1.0 1 0.5 maize 102 104 6.0 + 1.0 11 1.0 11 0.5 maize 87 90

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Herbicide antidote cultural Plant Zöldsúíy % of control The chemical name of the active substance Dose (Kg / ha) Serial number of the compound Dose spraying dressing spraying (Kg / ha) dressing (Kg / q) 2-Chloro-2 ', 6'-dimethyl-N- (methoxyethyl) -acetane 1d + 2-methoxy-4,6-bis (isopropylamino) -1,3,5-triazine 6.0 +0.8 - - - maize 57 57 6.0 +0.8 1 1 1.0 0.5 maize 102 104 6.0 +0.8 12 12 1.0 0.5 maize 78 80 2-chloro-2 ', 6'-dimethyl-N- (methoxymethyl) acetanilide + 2- (methylthio) -4- (ethylamino) -6- (isopropylamino) -1,3, 5-triazine 6.0 + 1.0 - - - maize 53 53 6.0 + 1.0 1 1 1.0 0.5 maize 104 100 6.0 + 1.0 13 13 1.0 0.5 maize 87 85 2-chloro-2 ', 6'-diethyl-N- (butoxymethyl) acetanilide + 2- (methylthio) -4- (methylamino) -6- (isopropylamino) -l, 3, 5-triazine 6.0 +0.5 - - - maize 57 57 6.0 +0.5 I 1 1.0 0.5 maize 107 106 6.0 +0.5 14 14 1.0 0.5 maize 91 95 2-chloro-2 ', 6'-diethyl-N- (butoxymethyl) acetanilide + 2-azido-4- (methylthio) -6- (isopropylamino) -1,3,5-triazine 6.0 +0.8 - - - maize 59 59 6.0 +0.8 1 1 1.0 0.5 maize 103 102 6.0 +0.8 15 15 1.0 0.5 maize 87 89 2-chloro-2 ', 6'-dimethyl-N- (isopropoxymethyl) acetanilide + 2-chloro-4- (diethylamino) -6- (isopropylamino) -1,3,5-triazine 6.0 + 1.0 6.0 + 1.0 6.0 + 1.0 1 1 16 1.0 1.0 0.5 0.5 maize maize maize 45 101 93 45 105 93 2-chloro-2'-methyl-6'-tert-butyl-N- (butoxymethyl) acetanilide + 2- (ethylthio) -4,6-bis (isopropylamino) -l, 3, 5-triazine 6.0 + 1.0 - · - - maize 48 48 6.0 + 1.0 1 1 1.0 0.5 maize 104 105 6.0 + 1.0 17 17 1.0 0.5 maize 85 89 2-chloro-N-isopropyl-acetanilide + 2-chloro-4- (isopropyl-amino) -6- (3-methoxy-propyl) amino-1,3,5-triazine 10.0 + 1.5 - -  - maize 70 70 10.0 + 1.5 1 1 Shoot 0.5 maize 108 105 10.0 + 1.5 18 1.0 0.5 maize 95 90 2-chloro-N-isopropylacetanilide + 2- (methylthio) -4- (ethylamino) -6- (tert-butylamino) -1,3,5-triazine 10.0 + 1.0 - - - maize 67 67 10.0 +1.0 1 1 1.0 0.5 maize 112 109 10.0 + 1.0 19 19 1.0 0.5 maize 98 93

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Herbicide Antidcrum cultural Plant green Weight % of control The chemical name of the active substance Dose (Kg / ha) Serial number of the compound Dose spraying dressing spraying (Kg / ha) dressing (Kg / q) 2-chloro-N- (l-methyl-2-propynyl) acetanilide +2 - (methylthio) -4- (isopropyl-amino) -6- (3- 6.0 + 1.0 - - - maize 65 65 methoxy-propylamino) -l, 3,5-triazine 6.0 + 1.0 1 1 1.0 0.5 maize 108 107 2-chloro-2'-methyl-6'-ethyl-N- (ethoxymethyl) acetanilide + 2-chloro-2 ', 6'-diethyl-N- (methoxymethyl) acetanilide 2-Cl + 4- 3.0 + 2.0 + 1.0 - - maize 62 62 - (ethylamino) -6- (isopropylamino) -1,3,5-triazine * 3.0 + 2.0 + 1.0 1 1 1.0 0.5 maize 107 108 2-Chloro-2 ', 6'-diethyl-N- (butoxymethyl) -acetanilide + 2-chloro-2'-ethyl-6'-methyl-N- (1-methyl-2-methoxy-ethyl) -acetanilide + 2-chloro-4- {ethylamino) -6- (isopropylamino) - 5.0 +2.5 +0.5 +0.5 - - - maize 67 67 -l, 3,5-triazine + 2- (methylthio) -4- (ethyl- amino) -6- (tert-butylamino) -l, 3,5- triazine 3.0 + 5.0 +0.5 +0.4 1 1 1.0 0.5 maize 106 103 2-chloro-N- (isopropyl acetanilide) + 2 Cl -2 ', 6'-diethyl-N- (methoxymethyl) acetanilide + 2-chloro-4- (cyclopropylamino) -6- (isopropylamino) -l, 3,5-triazine 2-Chloro + - 5.0 +2.5 +0.5 +0.5 - - - maize 67 67 4- (l-cyano-l-methyl-ethylamino) -6- (ethyl- amino) -l, 3,5-triazine + 5.0 + 2.5 + 0.5 + 0.5 1 1 1.0 0.5 maize 104 101

Example G) 40 B) S-ethyl-N, N-dipropyl-thiolcarbamate 2-chloro-4- (ethylamino) -6- (isopropyl) 50 weight ⁰ ',', Field Biological Experiment I. amino) -l, 3,5-triazine 8 dumbbells emulsifier: polyoxyethylene alkyl Based on the results of the greenhouse, -ether (Atlox 4873, Atlas Chemie) 4% by weight we have completed the formula (I), invention 45 dispersant: sodium lignin The compounds of the invention are of the thiolcarbamate type and the triazine sulfonate 3 weights ¹ /, ', Type I and chloroacetanilide type herbicidal combinations protective colloid: Iecithin 1 dumbbell to counteract the harmful effects of maize examining colloidal synthetic silica 5 dumbbells in field conditions. For experiments, WATER 29 dumbbells an aqueous colloidal suspension preparation having the following composition 100 dumbbells we prepared weasels by appropriate grinding. C) 2-Chloro-2'-methyl-6'-ethyl-N- (ethoxy) A) S-ethyl-N, N-dipropylthiolcarbamate 50% by weight methyl) acetanilide 40 dumbbells 2-chloro-4- (ethylamino) -6- (isopropyl 2-chloro-4- (ethylamino) -6- (isopropyl amino) -l, 3,5-triazine 8% by weight 55 amino) -l, 3,5-triazine 10 dumbbells N-dichloroacetyl-l-oxa-4-azaspiro N- (dichloroacetyl) -l-oxa-4-azaspiro - (4,5) -decane (Compound No. 1) 6% by weight - (4,5) -Dec. compound 7 dumbbells emulsifier: polyoxyethylene alkyl emulsifier: alkylphenol alkoxalate ether (Atlox 1690, Atlas Chemie) 4% by weight (Emulsogen ICL, Hoechst) 4% by weight dispersant: sodium lignin 60 dispersant: sodium lignin sulfonate 3 dumbbells sulfonate 3% by weight protective colloid: Iecithin 1 dumbbell protective colloid: Iecithin 1% by weight colloidal synthetic silica 3 dumbbells colloidal synthetic silica 5% by weight water 25 dumbbells WATER 30% by weight 100 dumbbells 65 100 dumbbells

-27181621

D) 2-Chloro-2'-methyl-6'-ethyl-N- (ethoxy)

-methyl-acetanilid 2-chloro-4- (ethylamino) -6- (isopropyl 40 wt / hr amino) -l, 3,5-triazine emulsifier: alkylphenol alkoxalate 10% by weight (Emulsogen ICL, Hoechst) Dispersant: Sodium Lignin 4 wt sulfonate 3 weight / h protective colloid: lecithin 1% by weight colloidal synthetic silica 8 wt / h WATER 34 dumbbells 100% by weight S-ethyl-N, N-dipropylthiolcarbamate 2-chloro-2'-methyl-6'-ethyl-N- (ethoxy 25 weight “oh -methyl-acetanilid 2-chloro-4- (ethylamino) -6- (isopropyl 20 wt / h -amino) -1,3,5-triazine 2-chloro-4- (l-cyano-l-methyl-ethylamino) -6- 5% by weight - (etylamino) -1,3,5-triazine 5% by weight

The size of the experimental plots was 20 m ² . To demonstrate the protective effect, formulations of the above formulations were sprayed at a dose close to twice the dose used in maize herbicide. As a control study of formulations "A", "C" and "E" containing the active ingredient of the present invention, formulations "B", "D" and "F" were the same as the herbicidal composition, but not containing the active ingredient of the present invention. at a similar dose.

The formulations were sprayed into the soil diluted with water at a volume of 300 L / ha and worked 5 cm deep into the soil. The cultivated areas were sown with SC 3269 maize. The effect of the preparation was evaluated 18 weeks after sowing. Both the harmful effect on maize and the herbicidal effect were studied. The basis for evaluation is internationally accepted based on visual evaluation

EWRC was a scale of values.

F) N- (dichloro-1-acetyl) -1-oxa-4-azaspiro-

- (4,5) -Dec. Compound Emulsifier: Mixture of Polyoxyethylene Alkyl Ether and Alkyl Phenol Alkoxalate 7 weight / h (Emulsogen I-40, Hoechst) Dispersant: Sodium Lignin 4 wt / h sulfonate 3% by weight protective colloid: lecithin 1 dumbbell colloidal synthetic silica 4 wt / h WATER 26% by weight 100% by weight S-ethyl N, N-dipropylthiolcarbamate 2-chloro-2'-methyl-6'-ethyl-N- 20 wt / h - (ethoxymethyl) acetanilide 2-chloro-4- (ethylamino) -6- (isopropyl 20 wt / h -amino) -1,3,5-triazine 2-chloro-4- (1-cyano-1-methylethyl) 5 wt / h -amino) -6-ethylamino-1,3,5-triazine emulsifier: polyoxyethylene alkyl aryl ether and alkyl phenol alkoxalate 5 dumbbells Blend (Emulsogen I-40, Hoechst) Dispersant: Sodium Lignin 4 wt / h sulfonate 3% by weight protective colloid: lecithin 1 weight / h colloidal synthetic silica 6 wt water 31 wt / h 100 wt%

Each value has the following meaning:

EWRC value- song Phytotoxic effects seen on crop plants Herbicidal action ° / o general impression First There are no 100 excellent Second very mild 98 very good Third 4th slight effect strong, but probably transient damage, product loss 95 good and unlikely 90 satisfying 5th uncertain phenomena 82 in question 6th detectable damage 70 unsatisfactory 7th severe damage 55 bad 8th very strong damage- very linking in 30 bad 9th total destruction 0 use- useless

The experiments were performed in 4 replicates, weighted averages of 4 replicates for the given EWRC.

The table above shows that all combinations without antidotes are excellent herbicides but are highly damaging to maize. However, compositions containing the same quantities of herbicide antidote and herbicidal action is practically _the same

Table X.

Sign of preparation weeds Fitotoxitás corn Dose (Kg / ha) Echinochloa crus-galli Digitaria sanguinalis Setaria viridis Chenopodium album Amaranthus reproflexus THE 20 2 2 1 2 3 1 B 20 2 2 1 2 3 6.5 C 12 1 1 1 2 2 1 D 12 1 2 1 2 2 6.5 E 20 1 2 1 2 4 1.5 F 20 1 2 1 2 4 7

-28181621 as a control herbicide combinations, but does not harm the maize at all.

Example H)

Field experiment II.

To test the effect of the compounds of formula (I) according to the invention as an antidote, an experiment was designed by spraying separately the separately formed antidote of formula (I) and the various combinations of the herbicides tested. In our experiment, we investigated whether the antidote and the herbicides were sprayed separately on the soil to ensure the protective effect of the antidote. As an antidote in each of the experiments, no. N- (dichloroacetyl) -1-oxa-4-azaspiro- (4,5-) decane. 70% w / w powder formulation.

The herbicidal combination used formulations "B", "D" and "F" in the previous example. The size of the experimental fields was 20 m ² . We set up our experiments as follows.

The soil was first treated with an antidote. For this purpose, an amount of 70% by weight of a wettable powder formulation of antidotes active compound, after dilution with 400 liters of water per liter of water, was sprayed onto the experimental parcel and rotated in a depth of 5 cm into the soil. (1.44 kg / ha at 70% w / w, corresponding to 1 kg / ha dose).

The experimental plot was then sown with 10 seeds of SC 3269 maize. One week after sowing, the amount of the given herbicide combination at the dose indicated in the table was sprayed onto the experimental plot after dilution with 300 L / ha water (preemergent treatment).

The effect of the preparations was checked one week after sowing. Both the harmful effect on maize and the herbicidal effect were studied. The assessment was based on an internationally accepted EWRC scale based on visual assessment.

The experiments were performed in 4 replicates, the EWRC values given are the weighted averages of the 4 replicates.

As a control, treatment with herbicidal combinations was carried out as described above, 1 week after sowing, but the soil was not treated with the exemplary antidote formulation prior to sowing.

XI. spreadsheet

Sign of preparation Dose (Kg / ha) weeds phytotoxicity corn Echinochloa CRUSSON-galli Digitaria sanguinalis Setaria viridis Chenopodium album Amaranthus retroflexus antidote B 1.44 20 2 2 1 2 3 1 B 20 2 1 1 2 3 6.5 antidote D 1.44 12 1 2 1 2 3 1 D 12 1 1 1 2 2 6.5 antidote F 1.44 20 1 2 1 2 4 1 ^F 20 1 2 1 2 4 6.5

It is clear from the above table that anti-dotamous treatment did not substantially reduce the herbicidal activity of the herbicidal combinations, but completely eliminated their phytotoxic effect on maize. According to our results, the antidoticidal composition according to the invention can effectively eliminate the harmful phytotoxic effect of the applied herbicides on maize even if the herbicidal and antidoticidal compositions are applied separately to the soil at different times.

Claims (1)

Herbicidal preparations with reduced phytotoxicity as active substances a) chloroacetanilide herbicides of general formula (IV) - in the formula R ⁶ is hydrogen or C 1-4 alkyl; R ⁷ is hydrogen or C 1-6 alkyl; A is C 1-4 alkyl, (C 1-4 alkyl) C 1-4 alkynyl, C 1-4 alkylene, or C 1-4 alkylene carbonyl; m is 0 or 1; and B is C 1-6 alkyl or 1,3-dioxolan-2-yl - Urea-type herbicides of the formulas 55 and VI: R ¹¹ is phenyl optionally substituted by one or more halo and / or C 1-4 alkyl and / or C 1-4 alkoxy or halo 60 substituted phenoxy or trifluoroethoxy; bcnztiazoI-2-yl; C 3-8 -cycloalkyl or 5- (C 1-6 -alkyl) -1,3,4-thiadiazol-2-yl; 65 R ^{12 is} hydrogen, C 1-4 alkyl -29181621 or (1-4C) alkoxy-benzoyl; R ¹³ is hydrogen, C 1-4 alkyl or phenyl; R ^{14 is} hydrogen, (C 1 -C 6) -alkyl, (C 1 -C 4) -alkoxy or (C 2 -C 5) -alkynyl - or b) thiolcarbamate-type herbicides of the formula II R ³ and R ⁴ each independently represent C 1-6 alkyl; or, taken together, represents a hexamethylene group; R ⁵ is C 1 -C 4 alkyl, benzyl or C 1 -C 4 -alkoxy substituted benzyl or di- or trichloroallyl, and triazine-type herbicides of the formula: R ⁸ is halogen, C 1-4 alkoxy, C 1-4 alkyl mercapto or azido; R ⁹ is (C 1-6 alkyl) amino or (C 1-4 alkoxy) (C 1-4 alkyl) amino; and R ¹⁰ is (C 1-6 alkyl) amino or (C 3-4 cycloalkyl) amino optionally substituted with cyano (C 1-4 alkyl) - or c) chloroacetanilide herbicides of formula IV wherein R ⁶ , R ⁷ , A, m and B are as defined above and triazine herbicides of formula V wherein R ⁸ , R ⁹ and R ^{10 has} the meaning given above - or d) a chloroacetanilide of formula IV wherein R ⁶ , R ⁷ , A, m and B have the same meanings as a urea of formula VI wherein R ¹¹ , R ¹² , R ¹³ and R ^{14 is} a herbicide of the above-defined type and a triazine of the formula V in which R ⁸ , R ⁹ and R ^{10 are} as defined above; obsession e) a chloroacetanilide of formula (IV) wherein R ⁶ , R ⁷ , A, m and B have the same meaning as a thiolcarbamate of formula (II): wherein R ³ , R ⁴ and R ⁵ herbicides of the above-mentioned type and triazine of the formula V in which R ⁸ , R ⁹ and R ^{10 are} as defined above; obsession f) chloroacetanilide of formula IV wherein R ⁶ , R ⁷ , A, m and B are urea of formula VI wherein R ¹¹ , R ¹² , R ¹³ and R ¹⁴ herbicides of the above-mentioned type and thiolcarbamate of the formula II in which R ³ , R ⁴ and R ^{5 are} as defined above; obsession g) thiolcarbamate of formula II: wherein R ³ , R ⁴ and R ^{5 are} urea of formula VI, wherein R ¹ , R ¹² , R ¹³ and R ^{14 are} as defined above - and herbicides of the triazine type represented by the general formula (V) wherein R ⁸ , R ⁹ and R ^{10 are} as defined above; obsession h) chloroacetanilide of formula IV: wherein R ⁶ , R ⁷ , A, m and B are urea of formula VI, wherein R ¹¹ , R ¹² , R ¹³ and R ^{14 is} a triazine of formula V wherein R ⁸ , R ⁹ and R ^{10 are} a thiolcarbamate of formula II wherein R ³ , R ⁴ and R ^{5 are} as defined above containing a mixture of herbicides, characterized in that from 0.1 to 50% by weight, based on the total weight of the herbicidal active compounds, of the antidotes of the formula I in which X is oxygen or S; n is 0 or 1; R ¹ and R ^{2 are the} same or different and are hydrogen or C 1 -C 2 alkyl, or R ¹ and R ^{2 taken} together are a butylene or pentylene group or a pentylene or hexylene group mono- or di-substituted with methyl, provided that when n is in d), e) and h) a mixture (I) of the antidote of formula wherein X is O or S - 0, eltérőjelentésű ^R1 and ^R2 are hydrogen or C1-2 alkyl group; n is 0; R ¹ and R ^{2 taken} together form a pentylene group optionally substituted with C 1 -C 4 alkyl, and the mixture of f) and g) is an antidote of formula I wherein X is O; n is 0 and R ¹ and R ² together form a pentylene group, together with the herbicidal active compound mixture in an amount of from 2.5 to 90% by weight, based on the total weight of the composition, of at least one solid and / or liquid carrier - preferably natural or synthetic powdered mineral or paraffin oil, and optionally a surfactant, preferably a fatty alcohol poly (glycol ether) or a fatty alcohol sulfonate.