DK156807B - Antagonist for protection of cultivated plants against the harmful effect of herbicidal compounds and its application - Google Patents

Description

DK 156807B

The present invention relates to an antagonist for the protection of culture plants against the damaging effect of herbicidal-active compounds of the thiolcarbnamate, triazine, chloroacetanilide, carbamide or phenoxyacetic acid type, and the antagonist of the invention is characterized in that the soin is antagonistically active. component contains a dichloroacetamide derivative of the general formula JCH2> n ^ CHf CH-10 (I) X - N - C - CHCl2

R R

Wherein X represents an oxygen or sulfur atom or a SO or SO 2 group, n is 0 or 1 and R 1 and R 2 are identical or different and represent hydrogen, alkyl or phenyl substituted by halogen, hydroxyl or nitro, or R1 and R2 together form a butylene, pentylene or hexylene group optionally substituted by one or two methyl groups, however, if n is 0, R1 and R2 do not mean hydrogen, alkyl or substituted phenyl.

The above antagonists reduce the phytotoxicity of the herbicides against cultured plants and are therefore suitable for their protection. The present invention also relates to the use of these antagonists together with herbicides of the aforementioned types for the selective control of undesirable weeds in an amount of the antagonistically active compound of formula (I) of 0.1-50% by weight of the herbicidal component.

It is well known to one of ordinary skill in the art that a substantial portion of the known herbicides are also harmful to the culture plants to be protected. The extent of this undesirable phytotoxic effect is highly dependent on the dose used and the conditions of use, e.g. weather and soil conditions.

Other herbicides are selective when used in small doses, but at a dose necessary for effective weed control.

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fighting, they have reduced selectivity and become detrimental to plant growth.

US Patent No. 3,131,509 proposes the use of 1,8-naphthalic acid and its derivatives, such as the anhydride, 5 esters and amides, to reduce the phytotoxicity of various herbicides.

According to IH-PS No. 165,736, the phytotoxicity of herbicidal compounds can be reduced by the addition of a Ν, Ν-disubstituted dichloroacetamide derivative in an amount of 0.0001-30% / by weight of the herbicide.

Most of the compounds widely used as antidotes belong to one of the above two compound classes, but they do not provide a definitive solution to this rather complicated problem. The herbicidal compounds whose phytotoxicity is to be reduced are chemically very different and, as a result, have different kinds of phytotoxic activities. It is also obvious that the different culture plants have different reactions when treated with different herbicides and therefore the scope of the known herbicides is very limited.

It is the object of the present invention to provide a novel compound class whose members are capable of reducing the phytotoxicity of certain herbicides and which are favorable for environmental protection. The novel compounds also ensure a more economical mode of use for known herbicides.

It has been found that novel dichloroacetamide amide derivatives of the general formula (I) are capable of reducing the phytotoxicity of herbicides of the triazine, carbamide, dichloroacetanilide and phenoxyacetic acid types.

More specifically, when a compound of the general formula (I) has been found to be mixed with at least one of the above herbicides in an amount of 0.1-50%, based on the weight of the herbicide, the herbicide preparations containing the resulting mixture, 35 are practically harmless to the culture plants while retaining their herbicidal activity. In another embodiment,

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In the form of the present invention, the same effect can be obtained when the seeds of culture plants prior to sowing are mixed with a compound of the general formula (I) (dressing) and when the weed control after sowing is carried out with a known herbicide which belongs to one of the above connection classes.

New compounds of the general formula (i) according to the invention are illustrated in the table below.

10 15 20 25 30 35

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It is clear from Table I that most of the novel compounds are in solid crystalline state under normal conditions and that only some of them are liquid at room temperature.

Chemical compounds of general formula (I) belong to acid amides and can be prepared by several alternative methods known in the art.

In a well-known process, compounds of general formula (I) are prepared by acylating a cyclic 10 amine or a site thereof with dichloroacetyl chloride in an indifferent solvent in the presence of an acid-binding agent [cf. DE-PS Nos. 2,350,547 and 2,350,800, W.R. Vaughan et al., J. Org. Chem. 26_, 145-148 (1961)]. As an inert solvent, a ketone such as acetone and methyl ethyl ketone, an aliphatic hydrocarbon such as hexane, an aromatic hydrocarbon, such as benzene, toluene or xylene, chlorobenzene, nitrobenzene, diethyl ether, dimethyl sulfoxide, or chlorinated aliphatic hydrocarbons, chloride or carbon tetrachloride. However, the acylation also takes place in the absence of an inert solvent. Suitable acid binding agents are e.g. organic bases, such as triethylamine, trimethylamine, pyridine and Ν, -Nthimethyl-aniline, but organic bases, such as alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal hydroxides, and other solutions thereof also used. The acylation is generally carried out at a temperature of between -50 and + 160 ° C, preferably between -20 and + 40 ° C.

Amines used as starting compounds are five- or six-membered heterocyclic compounds containing one nitrogen and one oxygen or sulfur atom, and the preparation of which has been described in numerous publications, such as J. Am. Chem. Soc. 7S_, 358-361 (1953), J.D.

Doughty et al: J. Am. Chem. Soc. 72, 2366 - 2367 (1950), and W.H. Watanabe: J. Am. Chem. Soc. 79_, 2833-2836 (1957).

Both five- and six-membered amines can be prepared by reacting a corresponding hydroxyalkylamine or mercapto-7.

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alkylamine or a hydrochloride thereof with an appropriate carbonyl compound in a solvent or without solvent, optionally in the presence of a catalyst, at room temperature or elevated temperature, optionally by continuous removal of the formed water.

Soin catalyst, e.g. basic catalysts such as alkali metal carbonates or acidic catalysts such as hydrogen chloride, hydrogen bromide or p-toluene sulfonic acid are used. Suitable solvents are various aliphatic hydrocarbons, e.g. hexane and petroleum ether, halo-generated derivatives thereof, such as methylene chloride and carbon tetrachloride, aromatic hydrocarbons, e.g. benzene, toluene and xylene, or derivatives thereof, e.g. chlorobenzene and nitrobenzene, as well as ethers or an excess amount of the carbonyl compound taking part in the reaction.

The reaction is carried out at a temperature of from 20 to 200 ° C. Using this reaction, five-membered cyclic amines are obtained by reacting aziridine with a corresponding carbonyl compound, optionally in the presence of hydrogen sulfide.

According to another method, compounds of general formula (I) are prepared from an N-dichloroacetylated hydroxyalkylamine or mercaptoalkylamine or the hydrochlorides thereof and a corresponding carbonyl compound under the reaction conditions described above.

In a third method, an N-nitroso derivative of the corresponding heterocyclic amines is reacted with dichloroacetyl chloride [cf. DE-PS No. 2,035,796, K.L. Hebenbrock et al., Justus Liebig, Ann. Chem. 765, 78-95 (1972)].

N-acylated heterocyclic amides can also be prepared by reacting a Schiff base prepared from a corresponding amino alcohol and carbonyl compound with dichloroacetyl chloride under the reaction conditions described above [M. Businolli: Il Farmaco (Pavia) Ed. Sci. 10, 35 127-134 (1955)].

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8

The preparation of the compounds of general formula (I) and their antidote activity is further illustrated in the following non-limiting examples.

Example 1

Preparation of N-dichloroacetyl-1-oxa-4-azaspiro [4/5] decane (Compound 1) From a boiling mixture of 64 g (0.645 mole) of cyclohexanone and 30 g (0.491 mole) of ethanolamine in 100 In benzene, the water that is formed is continuously distilled off. Cognition is continued until 8.8 ml of water is separated. The reaction mixture is then cooled and 55 g (0.55 mole) of a 40% aqueous sodium hydroxide solution is added followed by dropwise addition of 74 g (0.5 mole) of dichloroacetyl chloride while cooling from the outside with a mixture of seite and ice. The mixture is stirred for an additional 2 hours at room temperature and then washed with an aqueous hydrochloric acid solution 20 and then with water. Benzene is distilled off in vacuo from the resulting mixture. 10 g (0.4 mole) of greenish-white crystalline compound are obtained. Recrystallization from absolute ethanol gives a white crystalline product which melts at 105.5 - 107 ° C. The structure of the compound can be verified by IR1 spectrum analysis.

• Analysis:

Calculated: C = 47.63%, N = 5.50%, Cl = 28.12%.

Found: C = 47.12%, N = 5.70%, Cl = 28.56%.

Example 2

Preparation of N-dichloroacetyl-1-thia-4-azaspiro [4,5] decane (Compound 7) From a boiling mixture of 9.8 g (0.1 mole) of cyclohexanone and 7.7 g ( 0.1 mole of 2-mercaptoethylamine in 100 ml 9

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benzene continuously distills the water that is formed. The boiling is continued until 1.8 ml of water is separated. The reaction mixture is then cooled and 11 g of 40% aqueous sodium hydroxide solution is added followed by dropwise addition of 14.7 g (0.1 mole) of dichloroacetyl chloride while cooling from the outside with a mixture of seite and ice. The mixture is stirred at room temperature for an additional 2 hours and washed with aqueous hydrochloric acid solution and then with water. From the resulting neutral mixture, the benzene is distilled off in vacuo to give 17.2 g (0.064 mol) of white powder. Recrystallization from absolute ethanol gives a white crystalline product which melts at 149 - 151 ° C. The structure of the N-dichloroacetyl-1-thia-4-azaspiro [4,5] decane can be verified by IR spectrum analysis.

Analysis:

Calculated: C = 44.77%, N = 5.22%, S = 11.95%, Cl = 26.43%. Found: C = 44.51%, N = 5.31%, S = 12.15%, Cl = 26.29%.

Example 3 20

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

From a boiling mixture of 11.2 g (0.1 mole) of 4-methyl-25-cyclohexanone and 6.1 g (0.1 mole) of ethanolamine in 100 ml of benzene, the water formed is continuously distilled off. The boiling is continued until 1.8 ml of water is separated. The reaction mixture is then cooled and 8 g (0.1 mole) of pyridine is added followed by dropwise addition of 14.7 g (0.1 mole) of dichloroacetyl chloride while cooling from the outside with a mixture of seite and ice. When the process described in Example 2 is further followed, 20.7 g (0.078 mole) of pink oily product is followed / obtained. Recrystallization from absolute ethanol gives a white crystalline product which melts at 119-120 ° C.

The structure of the resultant compound can be verified by IR spectrum analysis.

10

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Analysis:

Calculated: C = 49.63%, N = 5.26%, Cl = 26.64%.

Found: C = 49.45%, N = 5.35%, Cl = 26.92%.

Example 4

Preparation of N-dichloroacetyl-1-oxa-5-azaspiro [5.5] undecane (Compound 19) From a boiling mixture of 17.6 g (0.18 mol) of cyclohexanone and 11.2 g ( 0.15 mol) of 3-aminopropanol in 50 ml of benzene is continuously distilled off the water that is formed. Cognition is continued until 2.7 ml of water is separated. The reaction mixture is then cooled and 16 ml (0.165 mole) of 40% aqueous sodium hydroxide solution is added followed by a subsequent, dropwise addition of 22.1 g (0.15 mole) of dichloroacetyl chloride with cooling from the outside with a mixture of acid and ice.

Further proceeding by the procedure described in Example 2 ------, 15.7 g (0.059 mol) of greenish-white crystalline product is obtained. Recrystallization from absolute ethanol gives a white crystalline compound which melts at 111 - 112 ° C. The structure of the resultant compound can be verified by IR spectrum analysis.

Analysis:

Calculated: C = 49.63%, N = 5.26%, Cl = 26.64%.

Found: C = 49.52%, N = 5.32%, Cl = 26.45%.

Example 5 30

Preparation of N-dichloroacetyl-1-thia-4-azaspiro [4,4] nonane (Compound 10)

From a boiling mixture of 8.4 g (0.1 mole) of cyclopentanone and 7.7 g (0.1 mole) of 2-mercaptoethylamine in 100 ml of benzene, the water formed is continuously distilled off.

11

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The boiling is continued until 1.8 ml of water is separated. The reaction mixture is then cooled and 8 g (0.1 mole) of pyridine is added followed by dropwise addition of 14.7 g (0.1 mole) of dichloroacetyl chloride while cooling off with a mixture of sait and ice.

Further proceeding in the manner described in Example 2, 21.6 g (0.085 mole) of yellowish, oily product is obtained. Recrystallization from n-hexane gives a white crystalline product which melts at 83 - 85 ° C. The structure 10 of the resultant compound can be verified by IR spectral analysis.

Analysis:

Calculated: C = 42.53%, N = 5.51%, S = 12.61%, Cl = 27.89%. Found: C = 42.35%, N = 5.45%, S - 12.80%, Cl = 27.56%.

15

Example 6

Preparation of N-dichloroacetyl-1-thia-4-azaspiro [4,5] decane-1-oxide (Compound 12) 13.41 g (0.05 mole) of N-dichloroacetyl-1-thia-4 aza-spiro [4,5] decane is dissolved in 100 ml of methylene chloride and to the resulting solution is added dropwise a solution of 9.15 g (0.053 mol) of n-chloroperbenzoic acid in 100 ml of methylene-chloride at a temperature of between -25 and -15 ° C. The reaction mixture is then stirred at room temperature for 2 hours and then cooled to 10 ° C. The insoluble compounds are filtered off and the filtrate is washed with two 30 ml portions of saturated sodium carbonate solution and then with water, dried over sodium sulfate and finally evaporated to dryness.

13.23 g of white crystalline product is obtained, yielding 93%. Recrystallization from absolute ethanol gives a white crystalline product which melts at 188 ° C (dec.).

35 12

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Analysis:

Calculated: C = 42.26%, H = 5.32%, O = 11.26%, N = 4.93%,

Cl = 24.95%, S = 11.28%.

Found: C = 42.18%, H = 5.30%, O = 11.35%, N = 4.98%, Cl = 24.90%, S = 11.30%.

The structure of the resulting compound can be verified by IR spectrum analysis.

Example 7 10 "Preparation of N-dichloroacetyl-1-thia-4-azaspira [4,5] decane-1,1-dioxide (Compound 13) - 13.41 g (0.05 mole) of N-dichloroacetyl -1-Thia-4-aza-15 spiro [4,5] decane is dissolved in 150 ml of methylene chloride and a solution of 18.12 g (0.105 mol) of m-chloroperbenzoic acid in 200 ml of methylene chloride is added dropwise at a temperature between 0 and 3 ° C. The reaction mixture is then stirred at room temperature for 1 hour and boiled for an additional 1 hour.

It is then cooled to 5 ° C, the precipitated solid is filtered off and washed with 50 ml of methylene chloride. The filtrate is washed with two 50 ml portions of saturated sodium carbonate solution and then with water, dried over anhydrous sodium sulfate and finally evaporated to dryness. 13.7 g (91%) of 25 yellowish-brown crystalline product is obtained, which is then recrystallized from acetone using activated charcoal for decolorization. The melting point of the resulting white crystalline product is 180 - 181 ° C (dec.).

Calculated: C = 40.00%, H = 5.12%, O = 15.99%, N = 4.67%,

Cl = 23.66%, S = 10.68%.

Found: C = 40.10%, H = 5.08%, O = 16.03%, N = 4.70%,

Cl = 23.60%, S = 10.72%.

The structure of the resulting compound can be verified by IR spectrum analysis.

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All the other compounds listed in Table I, together with their physical characteristics, can be prepared by analogy.

Some representatives of the herbicides whose phytotoxicity is diminished under the influence of the compounds of general formula (I) are listed below: S-ethyl-N, N-dipropylthiocarbamate, S-propyl dipropylthiocarbamate, S-ethyl-diisobutylthiocarbamate, S-2,3,3-trichloroallyl diisopropylthiocarbamate, S-ethyl cyclohexylethylthiocarbamate, 2-chloro-2 ', 6'-N- (methoxymethyl) acetanilide, 9-ethylhexahydro-1H-azepine-1-carbothioate, 2 -chloro-N-isopropylacetanilide, N, N-diallyl-2-chloroacetamide / S-4-chlorobenzyl diethylthiocarbamate 2-chloro-4-ethylamino-6-isopropylamino-s-triazine, 2-chloro-4,6-bis (ethylamino ) -as-triazine ,.

2- (4-Chloro-6-ethylamino-s-triazin-2-yl-amino) -2-methyl-propionitrile, 2-chloro-4-cyclopropylamino-6-isopropylamino-s-triazine, 2,4-dichlorophenoxyacetic acid , 3- (31,41-Dichlorophenyl) -1-methyl-1- (n-butyl) urea, 2-chloro-21-ethyl- 61-methyl-N- (1-methyl-2-methoxyethyl) - -acetanilide, 2-chloro-21,6'-diethyl-N- (1,3-dioxolan-2-yl-methyl) -acetanilide, 2-chloro-2 ', 6'-diethyl-N- (ethoxycarbonylmethyl) - acetanilide, 2-chloro-N-ethoxymethyl-2'-methyl-6'-ethyl-acetanilide, 2-chloro-N- (21-methoxyethyl) -2 ", 6" -dimethyl-acetanilide, 2-chloro-N -butoxymethyl-2 ', 61-diethyl-acetanilide, 2-chloro-N- (2 "-methoxy-1" -methyl-ethyl) -2'-methyl-61-ethyl-acetanilide, 2-chloro-N-isopropoxymethyl -2 ', 6'-dimethylacetanilide, N, N-hexamethylene-5-ethyl-thiolcarbamate, N- (3-chlorophenyl) -N'-methyl-N1-methoxyurea, 14

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N- (3,4-dichlorophenyl) -N'-methyl-N1-methoxyurea, N- (3-chloro-4-bromophenyl) -N'-methyl-N'-methoxyurea, 2-butylamino-4-chloro-6 -ethylamino-s-triazine, 2-chloro-4,6-bis-isopropylamino-s-triazine, 2-methylmercapto-4,6-bis-isopropylamino-s-triazine, 2-methylmercapto-4-ethylamino-6- tert.butylamino-s-triazine, 2-tert.butylamino-4-ethylamino-6-methoxy-1,3,5-triazin, 4-amino-6-tert.butyl-3-methylthio-4,5-dihydro -1,2,4-triazine-5-one, 2,4-dichlorophenoxyacetic acid, 274-dichlorophenoxypropionic acid, .........

2,4-dichlorophenoxyacetic acid, 2-methyl-4-chlorophenoxyacetic acid, 2,4,5-trichlorophenoxyacetic acid and the mixtures of the above compounds.

Dichloroacetamide derivatives of the general formula (I) may be formulated alone or together with one or more of the herbicides for which some representatives are indicated above for solid or liquid agents by conventional techniques widely used in the preparation of plant protection products. The crystalline compounds of general formula (I) is converted into wettable powders by the following process: Wettable powder: 70.0% compound of the general formula (I) 17.0% kaolin 8.0% activated silicic acid 2.5% fatty alcohol sulfonate 2.5% lignin sulfonic acid Na.

By mixing the above components in the given amounts in an "Alpine" mill, a wettable powder agent is obtained which is ready for use. When a herbicide active ingredient is also used, 50% of a herbicide and 20% of a compound of the general formula (I) are mixed with the other 35 ingredients.

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When it is intended to use the compounds of general formula (I) to reduce the phytotoxicity of known herbicides prior to sowing by mixing the active ingredients with the seeds, advantageously 5 talc are used which carry in an amount of 20-30%.

Some of the compounds of general formula (I) are liquid at room temperature and can therefore be advantageously formulated in the form of emulsifiable concentrates. A typical emulsifiable concentrate consists of the following ingredients: 10 Emulsifiable concentrate I: 20 - 50% compound of the general formula (I) 74 - 45% solvent (eg xylene) 9% polyoxyethylene alkyl ether emulsifier. The composition of another emulsifiable concentrate 15 is given below:

Emulsifiable concentrate II: 7% compound (I) .75% EPTC 13% xylene 5% polyoxyethylene alkyl ether emulsifier.

Of course, crystalline compounds can also be formulated as emulsifiable concentrates. Emulsifiable concentrates are particularly advantageous when the phytotoxicity of a liquid herbicide (eg EPTC) is to be reduced by a compound of the general formula (I).

Emulsifiable concentrate III: 2-chloro-N- (methoxymethyl) -2 ', 6'-diethyl-acetanilide 50% N-dichloroacetyl-1-thia-4-azaspiro [4,5] -30-decane 8% polyoxyalkylacyl emulsifier 5% xylene 37% 35 16

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Granules: S-propyl-N, N-diisobutylthiol carbamate 5% N-dichloroacetyl-1-oxa-5-azaspiro [5.5] undecane 0.5% pumice stone 94.5%

Compounds of general formula (I) exert their antidote activity when sprayed together with an inert herbicide, either formulated together or in the form of a container mixture prepared prior to spraying, but treatment can also be carried out prior to spraying with herbicide. . In an advantageous embodiment of the treatment, seeds are treated with a formulation containing a compound of the general formula (I) prior to sowing, and the herbicidal agent is sprayed onto the ground immediately before or after sowing.

The following examples illustrate the effect of the compounds of general formula (I) in combination with "Afalone" [N- (3,4-dichlorophenyl) -N'-methyl1-N'-methoxy-urine], "Eptam" [N , N-dipropyl-5-ethylthiolcarbamate], "Sencor" [4-amino-5-tert-butyl-4,5-dihydro-3-methylthio-1,2,4-triazine-5-one] and "Lasso" [2-chloro-N- (methoxymethyl) -21,6'-diethylacetanilide]. For comparison, 1,8-naphthalic anhydride and N, N-diallyl-2,2-dichloroacetamide, both known antidotes, have been used. The target of phytotoxicity is the green-25 weight of the treated plants. 100% is the weight of plants grown exclusively using mechanical weed control.

Example 8 30

The deleterious effect of "Afalone" is observed in sunflower cultures. The extent of the reduction of this detrimental effect, when compounds of general formula (I) are also used, is also tested.

35 Four successive trials are carried out at locations every 20 m. "Afalone 50 WP" is used at a dose of 17

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5 kg of active ingredient per ha. Antidotes are sprayed in the fields parallel to "Afalone" in the form of aqueous suspensions. The results obtained are given in the table below.

Table II

Dose (kg / ha) of antidote 0.5 1.0_2.0

Green weight expressed in% 10 calculated on the control "Afalone" 41 41 41 "Afalone" + 1,8-naphthalic anhydride 58 69 75 15 "Afalone" + N, N-diallyl-2,2- _-dichloroacetamide_48_51_67 "Afalone" + compound 2 78 92 95 "Afalone" + compound 7 67 89 90 "Afalone" + compound 15 75 93 102 20 "Afalone" + compound 17_81_95_99

Control (mechanical weed control) _100_100_100

It can be seen unequivocally from the measurement of the green weight of sunflowers that the heterocyclic dichloro-acetamides in question reduce the phytotoxicity of "Afalone" significantly better than either 1,8-naphthalic anhydride or N, N-diallyl-2,2 -dichloracetamid. It can also be seen that compound 17 has a practically 100% antidote effect.

30

Example 9

In field experiments conducted in a practically nautical manner as described in Example 8, the phytotoxicity of 5 kg / ha "Afalone" is tested on sunflower plants whose seeds are treated with antidotes according to the invention and 18

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known antidotes prior to sowing. The results of these experiments are compared with the results obtained by mechanical weed control (100%). It turns out that smaller doses of the test compounds are sufficient to achieve the same effect as in the experiments of Example 8. The numerical results are shown in Table III below.

Table III

10 Dose (kg / ha) of antidote 0 / 25_0f50_1 / 00

Green weight expressed as% calculated on control 15 "Afalone" _41_41 41 1/8-Naphthalic anhydride + "Afalone" 57 69 75 N, N-diallyl-2,2-dichloroacetamide + "Afalone" _62_71_75 20 "Afalone" + compound 2 89 95 98 "Afalone" + connection 7 78 86 90 "Afalone" + connection 15 90 94 96 "Afalone" + connection 17_92_98_100

Control 25 (mechanical weed control) _100_100_100

Within the accuracy of the measurement, the results are not significantly different from the results obtained in Example 8, although smaller doses of antidote are used.

30

Example 10

The deleterious effect of "Eptam" is observed in maize cultures. The extent of the reduction of this undesirable effect, when compounds of the invention are also used, is also tested.

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Four successive field trials are conducted on fields of 20 m each. The tested corn belongs to the "Beke 270" blend. 13 liters / ha of liquid "Eptam 6 E" herbicide and various doses of antidote are sprayed onto the fields in form 5 by a container mixture prior to sowing. The results obtained are given in Table IV below.

Table IV

Dose (kg / ha) of antidote 0.5_1 ^ 0_2.0

Green weight expressed in% calculated on control 15 "Eptam" _48_48_48 "Eptam" + 1,8-naphthalic anhydride 60 64 70 "Eptam" + N / N-diallyl-2,2-di-chloroacetamide_69_84_92 ^ 20 "Eptam" + compound 1 98 102 105 "Eptam" + compound 2 90 98 99 "Eptam" + compound 3 94 97 100 "Eptam" + compound 7 97 100 100 "Eptam" + compound 9 92 97 98 25 "Eptam" + compound 17 98 100 100 "Eptam" + connection 19_96_98_102

Control (mechanical weed control) _100_100_100 30. It is clear from the above results that five of the seven tested heterocyclic dichloroacetamides completely eliminate the phytotoxic effect caused by "Eptam", but also the remaining two compounds have at least the same effect Ν-dichloroacetamide ("Ardicane"), widely used for this purpose.

Example 11 20

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Field experiments are carried out in practically the same manner as described in Example 10, with the one difference being that the 5 seeds are treated with different doses of antidote before arriving in a soil treated with 13 liters / ha of liquid "Eptam 6 E". . The results obtained when measuring the green weight of the plants are shown in Table V. below.

Table V

Dose (kg / q fr0) 0.25_0.50_1.00

Green weight extracted in% 15 calculated on the control "Eptam" _48_48_48 1,8-Naphthalic anhydride + "Eptam" 68 70 72 20 N, N-diallyl-2,2-dichloroacetamide + "Eptam" _69 75_80 "Eptam" + compound 1 98 100 100 "Eptam" + compound 2 95 97 97 "Eptam" + compound 3 97 98 102 25 "Eptam" + compound 7 98 102 105 "Eptam" + compound 9 90 95 95 "Eptam" + compound 17 95 98 98 " Eptam "+ connection 19_97_100_103

control

30 (mechanical weed control) _100_100_10Q

It is clear from the results set forth in Table V that compounds 1, 3, 7 and 19 virtually completely eliminate the deleterious effect of "Eptam", although smaller doses of antidote are used.

Example 12 21

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The effect of compounds of the general formula (1) on the phytotoxic effect of "Sencor" in soybean cultures is tested. Soybeans are treated with a suspension containing 1.5 kg / ha "Sencor" and various doses of antidote immediately after sowing. The results obtained are given in Table VI below.

Table VI

10

Dose (kg / ha) of antidote 0.5_1 ^ 0_2.0

Green weight expressed in% calculated on control 15 "Sencor" _17_17_17 "Sencor" + 1,8-naphthalic anhydride 41 41 52 "Sencor" + N, N-diallyl-2,2-di-2 g _chloroacetamide_20_21_26 "Sencor" + compound 1 42 65 72 "Sencor" + compound 7 48 70 76 "Sencor" + compound 8 45 68 76 "Sencor" + compound 17_48_71_82: 25 Control (mechanical weed control) _100_100_100

It is clear from the above results that compounds of the general formula (I) have a significantly better antidote effect than either 1,8-naphthalic anhydride or N, Ν-diallyl-dichloroacetamide.

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Example 13

Other experiments are practically performed as described in Example 12 except that soybean seed is treated with antidote and that "Sencor" is sprayed on the ground immediately after sowing at a rate of 1.5 kg / ha.

The results obtained are given in Table VII below.

Table VII

Dose (kg / q fr0) 0.25_0.50_1.0

Green weight expressed in% 15 calculated on the control "Sencor" _17_17_17 "Sencor" + 1,8-naphthalic anhydride 51 64 70 20 "Sencor" + N, N-diallyl-2,2-di-chloroacetamide_26_28_51 "Sencor" + compound 1 52 75 80 "Sencor" + connection 7 58 79 87 "Sencor" + connection 8 55 75 82 25 "Sencor" + connection 17_61_82_92

Control (mechanical weed control) _100_100_100

The above results illustrate that "Sencor" 30 has virtually no detrimental effect on soy pre-treated with compounds of general formula (I), especially compound 17, while 1,8-naphthalic anhydride and N, N -dially1-2,2-dichloroacetamide has a much weaker antidote.

35

Example 14 23

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Attempts are being made to ascertain the phytotoxic effect of "Lasso", an agent containing 2-chloro-5-N- (methoxymethyl) -2 ', 6'-diethylacetanilide as active ingredient, in animal cultures and to observe, how this undesirable effect is affected by the addition of compounds of general formula (I).

Four successive field trials are carried out at 2 10 sites at 20 m each with 4.5 liter / ha doses of "Lasso 48 EC".

Wettable powder formulations containing a compound of general formula (I) as active ingredient are suspended in water and then mixed with an aqueous emulsion of "Lasso 48 EC" in an amount corresponding to the doses given in Table VIII below. The mixture thus obtained is applied to the soil after sowing the sorghum, but prior to its emergence (pre-emergent treatment). The results are assessed by comparing the green weights of four weeks of garnish plants with the green weights of the control treated with mechanical weed control.

Table VIII

Dose (kg / ha) active ingredient 25.0

Green weight expressed in%

Treatment _._ based on the control "Lasso 48 EC" _37_37_37 30 "Lasso 48 EC" + 1,8-naphthalic anhydride 61 65 70 "Lasso 48 EC" + N, N-diallyl-2,2-________-dichloroacetanilide 72_78_82 "Lasso 48 EC "+ compound 1 95 97 102 35" Lasso 48 EC "+ compound 2 80 87 92" Lasso EC "+ compound 7 90 95 98

Table VIII (continued) 24

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Dose (kg / ha) active ingredient 0 / 5_1.0 2.0 5 Weight weight expressed in%

Processing_calculated on control "Lasso 48 EC" + compound 12 75 78 83 "Lasso 48 EC" + compound 13 92 98 100 "Lasso 48 EC" + compound 14 90__96_9i8 10 Control

(mechanical weed control) _100_1QQ_1QQ

Example 15 15 Field experiments are carried out in practically the same manner as described in Example 10 with the one difference that seeds are treated with different doses of antidote with the general formula (I) prior to sowing and that after sowing, a dose of 4.5 liters / ha of "Lasso 48 EC" in the fields.

20 The results obtained by measuring the green weight of four weeks of garnish plants, expressed in% by weight of the control, are given in Table IX below.

Table IX

2 R

Dose (kg of active ingredient per q fr0) 0.25_0.50_1.0

Green weight expressed in%

Calculated on control 30 "Lasso 48 EC" _37_37_37 "Lasso 48 EC" + 1,8-naphthalic anhydride 68 71 73 "Lasso 48 EC" + N, N-dially1-, 2,2- '-dichloroacetamide_75_ 80 85 " Lasso 48 EC "+ compound 1 98 105 110 25

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Example 16

Comparative experiments are carried out with maize as culture plants in the field indicated in Example 10, but with the compound N-5-dichloroacetyl-2,2-dimethyl-1,3-oxazolidine (compound A) known in the Danish Patent Specification No. 143,583. and with "Eradicane" (75.5% by weight S-ethyl-N, N-dipropyl-thiol carbonate + 6.8% by weight Ν, Ν-diallyl-dichloroacetamide) as control herbicide. The antagonists are available as a 70% wettable powder of the above composition which is formulated for use with the herbicide and sprayed as a container mixture on the test fields. In all experiments "ΕΡΤΑΜ 6E" is used as a herbicide in one volume of 13 liters / ha and the control herbicide is sprayed in the same amount.

The results are shown in Table X below.

Table X

Dose GrOweight Weigh Phyto-

Antagonist (kg / ha) (% of control) toxicity 20

None - 35.0 9

Control Herbicide 101.6 1

Compound A (known) 0.71 81.6 4 25 1.42 96.2 1

Compound 0 0.71 118.6 1. 1.42 125.2 1

Compound 5 0.71 95.4 1 30 1.42 103.5 1

Compound 6, 7l 87.2 2 1.42 99.2 1

Compound 7 0.71 105.4 1 1.42 113.2 1 35 Compound 12 0.71 112.1 1 1.42 121.2 1

Compound 13 0.71 108.5 1 1.42 119.5 1

Compound 19 0.71 102.1 1 40 1.42 106.5 1

Mechanical weed control - 100 1 26

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From Table X it will be seen that the antagonists of formula (I) are substantially better than the known compound.

No single antagonist has any influence on the herbicidal action against the weed species. The indicated phytotoxicity is on a scale where the highest number indicates the most severe damage to the culture plants.

Example 17

Another comparative experiment is carried out with the same antagonists as in Example 16, but here the container mixture of herbicide + antagonist is sprayed only 4 days after sowing the maize. In this experiment, the highly phytotoxic herbicide "Acetochlor" (active component 2-chloro-2'-methyl-6'-ethyl-N- (ethoxymethyl) -acet-anilide) used for maize is highly potent.

The maize (corn grain, JX-62 ") is seeded in clay sandy soil with a content of organic matter of 1.4% on parcels with a size of 20 m2, and for each antagonist and the control (herbicide alone) 4 separate experiments are carried out.

The spraying is carried out in such a way that a quantity of liquid equal to 400 liters / ha is applied which contains herbicide corresponding to 8 liters / ha. The assessment takes place 18 weeks after the sowing according to a phytotoxicity scale (EWRC), where a higher number corresponds to a stronger crop plant damage.

The results are shown in Table XI below, where the indicated phytotoxicities are the average of the 4 trials for each antagonist (amount).

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Table XI

Dose of Phytotoxic

Antagonist (kg / ha) Safety 5 None - 7

Compound A 0.71 5 (known) 1.42 3 10 Compound 1 0.71 1 1.42 1

Compound 5 0.71 3 1.42 2

Compound 6 0.71 2 15 1.42 1

Compound 7 0.71 1 1.42 1

Compound 12 0.71 2 1.42 1 20 Compound 13 0.71 3 1.42 2

Compound 19 0.71 4 1.42 2 25 Mechanical weed control

It is clear from Table XI that by using an "Acetochlor" dose higher than the usual 30 (5 liters / ha), no sufficient antagonist effect is obtained with the low dose of the known compound, and that even the high dose produces phytotoxic symptoms. It will also be seen that with the antagonists of the invention a significantly better effect is obtained, in several cases no phytotoxicity even at the low dose.

Claims (4)

An antagonist for the protection of culture plants against the damaging effect of herbicidal active compounds 5 selected from thiolcarbamate, triazine, chloroacetanilide, carbamide and phenoxyacetic acid type compounds, characterized in that it as an antagonistically active ingredient contains a dichloroacetamide derivative of the general formula 10 (CHO)> 2 'CHf CH ~ (I) X Ή - C - CHCl₂ 15 / \ / V where X means an oxygen or sulfur atom or a SO or SC n is 0 or 1 and R 1 and R 2 are identical or different and mean hydrogen, alkyl or phenyl substituted with halogen, hydroxyl or nitro, or r and R 2 together form a butylene, pentylene or hexylene group 7 optionally substituted with one or two methyl groups, however, if n is 07 R 10 and R 2 does not mean hydrogen, alkyl or substituted phenyl. Use of the antagonist according to claim 1 with one or more thiol carbamate, triazine, chloroacetani-lid, carbamide or phenoxyacetic acid herbicides to selectively control undesirable weeds in an amount of the antagonistically active compound of formula ( I) of 0.1-50% by weight of the herbicidal component. Use according to claim 2, characterized in that, on the ground, simultaneously or successively apply separate compositions containing respectively a compound 35 of the general formula (I), wherein X, n, R1 and R2 are as defined in claim 1, and the herbicide active ingredient. DK 156807 B Use according to claim 2, characterized in that seeds of culture plants are treated with a composition containing a compound of the general formula (I), wherein X, n, R1 and R2 have the meaning given in claim 1, prior to 5. sowing and that the compositions containing at least one of the herbicidal compounds as active ingredient are applied to the soil after sowing.