CS207775B2 - Selective herbicide means - Google Patents

Description

The invention relates to a selective thiocarbamate-based herbicidal composition. It comprises as active ingredient at least one herbicidal compound selected from the group consisting of thiocarbamate, triazine, chloroacetanilide, carbamide or phenoxyacetic acid, in admixture with 0.1 to 50% by weight of the diacetone derivative of the formula I (chA / c) _from L // I 'II C

in which

X is an oxygen or sulfur atom, or an SO or SO2 group, n is zero or 1 a

R1 and R2 are each hydrogen, C1-C4alkyl or phenyl substituted with hadogen, hydroxy or nitro, or R1 and R2 together form a butylene, pentylene or hexylene group, optionally substituted with one or two methyl groups, provided that when n is zero, R 1 and R 2 are other than hydrogen, C 1 -C 4 alkyl or substituted phenyl.

The above compositions have reduced phytotoxicity against cultivated plants and are therefore suitable for protection against unwanted weeds. The process of using said compositions for the above purpose is also within the scope of the present invention.

It is well known to those skilled in the art that a substantial proportion of the known herbicides also harm the cultivated plants to be protected. The extent of this adverse effect is strongly dependent on the dose used and the conditions of application, for example weather and soil conditions. Other herbicides are selective when used in small doses, but at the dose required for effective weed control, they have reduced selectivity and are detrimental to plant growth.

U.S. Pat. No. 3,131,509 proposes to use 1,8-naphthalenic acid and derivatives thereof such as anhydride, esters and amides to enhance the phytotoxicity of various herbicides.

According to the teachings of Hungarian patent specification 165,736, the phytotoxicity of the herbicidal compounds can be reduced by the addition of

Ν, Ν-disubstituted dichloroacetamide

207 7 7 5 of the derivative in an amount of 0.0001 to 30% based on the weight of the herbicide.

Most of the compounds widely used as antidotes belong to one of the above two classes of compounds, but do not provide a definitive solution to this rather complex problem. Herbicidal compounds whose phytotoxicity is increased are chemically very different and therefore have different types of phytotoxic effects. It is also evident that different cultivated plants have different reactions when treated with different herbicides and therefore the range of application to known herbicides is severely limited.

The present invention relates to a new class of compounds whose members are able to reduce the phytotoxicity of certain herbicides and are advantageous with respect to environmental protection. The novel compounds also provide a more economical way of applying known herbicides.

It has been found that the novel dichloroacetamide derivatives of the formula I are capable of reducing the phytotoxicity of the triazine, carbamide, dichloroacetanilide and phenoxyacetic acid herbicides. In particular, it has been found that when the compound of formula I is mixed with at least one of the above-mentioned herbicides in an amount of 0.1 to 50% by weight of the herbicide, the obtained herbicidal compositions containing the mixture are practically harmless to the cultivated plants while preserving their herbicidal effect.

In another aspect of the present invention, the same effect can be achieved when the seeds of the cultivated plants are mixed with the compound of formula I (pickling) before sowing and after sowing the weeds are destroyed by a known herbicide belonging to one of the above classes of compounds.

The novel compounds of the formula I according to the invention are illustrated by the following Table 1.

Table 1

Merge- nina number X n Rl Rz Compound Physical constant (melting point ° C, refractive index) 1 0 0 pentylene N-dichloroacetyl-1-oxa-4-azaspiro [4,5] dean 105.5 to 107 2 0 0 1‘-methyl- pentylene N-dichloroacetyl- -10-methyl-1-oxa-4-azaspiro [4,5] dean 100 to 102 3 0 0 3‘-methyl- pentylene N-dichloroacetyl-8-methyl-1-oxa-4-azaspiro [4,5] dean 119 to 120 4 0 0 1,5‘-dimethyl- pentylene N-dichloroacetyl- -6,10-dimethyl-1-oxa-4-azasplro [4,5] dean n _D ²⁶ : 1.5217 5 0 0 butylene N-dichloroacetyl-1-oxa-4-azaspiro [4.4] nonane 79 to 80 6 0 0 hexylene ' N-dichloroacetyl-1-oxa-4-azaspiro [4.6] undecane 81 to 82 7 with 0 pentylene N-dichloroacetyl- -1-thia-4-azaspir [4,5] dean 149 to 151 8 with 0 1‘-methyl- pentylene N-dichloroacetyl-10-methyl-1-thia-4-azaspiro (4,5) dean 106 to 109 9 with 0 3‘-methyl- pentylene N-dichloroacetyl-8-methyl-1-thia-127 to 129 -4-azaspiro [4,5] dean 10 with 0 butylene N-dlchloracetyl- -1-thia-4-azaspiro [4.4] nonane 83 to 85 11 with 0 hexylene N-dichloroacetyl- 96 to 99

-1-thia-4-azaspiro [4.6] undecane

Merge- nina number 5 R2 8 X n Rl Compound Physical constant (melting point ° C, refractive index) 12 SO 0 pentylene N-dichloroacetyl- -1-thia-4-azaspiro [4.5] decane-1-oxide 188 13 SO2 0 pentylene N-dlchloracetyl- -1-thia-4-azaspiro [4,5] decane-1,1-dioxide 180 to 181 14 0 1 H H N-dichloroacetyltetrahydro- -1,3 (2H) oxanine n _D ^26: 1.5168 15 Dec 0 1 CHs CHs N-dichloroacetyl- -2,2-dimethyltetrahydro- -1,3 (2H) oxazine n _D ²⁶ : 1.5070 16 0 1 CHs C2H5 N-dichloroacetyl- -2-methyl-2-ethyltetrahydro- -1,3 (2H) oxazine n _D ^zs : 1.4919 17 0 1 pentylene N-dichloroacetyl- -1-oxa-5-azaspiro [5.5] undecane 111 to 112 18 0 1 Methyl-methyl- pentylene N-dichloroacetyl-11-methyl-1-oxa-5-azaspiro [5.5] undecane 136 to 138 19 Dec 0 1 3‘-methyl- pentylene N-dichloroacetyl-9-methyl-1-oxa-5-azaspiro [5.5] undecane 115 to 118 20 May 0 1 butylene N-dichloroacetyl-1-oxa-5-azaspiro [5.4] dean 62 to 64 21 0 1 hexylene N-dichloroacetyl- n _D ^26: 1.5012

-1-oxa-5-azaspiro [5.6] dodecane

It can be clearly seen from Table 1 that most of the novel compounds are solids, in a crystalline state under normal conditions, and only some of them are liquid at room temperature.

The chemical compounds of formula (I) are acid amides and can be prepared by several alternative methods known in the art.

According to a well known process, the compounds of formula I are prepared by acylating a cyclic amine or a salt thereof with dichloroacetylachloride in an inert solvent in the presence of an acid-binding agent [see German patents 2,350,547 and 2,350,800; W. R. Vaughan et al., J. Org. Chem. 28, 145-148 (1961). As an inert solvent, a ketone such as acetone or methyl ethyl ketone, an aliphatic hydrocarbon such as hexane, an aromatic hydrocarbon such as benzene, toluene, xylene, chlorobenzene, nitrobenzene, diethyl ether, dimethylsulfoxide or chlorinated aliphatic hydrocarbons such as methyl chloride or carbon tetrachloride may be used.

However, the acylation also takes place in the absence of an inert solvent. Suitable acid binding agents are, for example, organic bases such as triethylamine, trimethylamine, pyridine, Ν, Ν-dimethylaniline, but inorganic bases such as alkali metal carbonates, acid carbonates and hydroxides and suitable solutions thereof may also be used. The acylation is usually carried out at a temperature between -50 and 160 ° C, preferably between -20 and 40 ° C.

The amines used as starting compounds are 5- or 6-membered heterocyclic compounds containing one nitrogen atom and one oxygen or sulfur atom. The preparation of these compounds is described in a number of publications, such as in J. Am. Chem. Soc. 75, 358-361 (1953); J. D, Doughty et al., J. Am. Chem. Soc. 72, 2366-2367 (1950); W. H. Watanabe, J. Am. Chem. Soc. 79, 2833-2836 (1957).

Both 5- and 6-membered amines can be prepared by reacting the corresponding hydroxy alkylamine or mercaptoalkylamine or their hydrochloride with the appropriate carbonyl compound, in a solvent or in the absence of a solvent, optionally in the presence of a catalyst, at room temperature or elevated temperature and optionally with continuous removal of water.

As the catalyst, basic catalysts such as alkali metal carbonates or acid catalysts such as hydrogen chloride, hydrogen bromide or p-toluenesulfonic acid can be used. Suitable solvents are various aliphatic hydrocarbons such as hexane, petroleum ether or halogenated hydrocarbon derivatives such as methylene chloride or carbon tetrachloride, aromatic hydrocarbons such as benzene, toluene or xylene or derivatives thereof such as chlorobenzene or nitrobenzene, as well as ethers or excess carbonyl compound involved in the reaction .

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

In another method, compounds of formula (I) are prepared starting from N-dichloroacetyl hydroxylamine or mercaptoalkylamine or their hydrochlorides and the corresponding carbonyl compound using the reaction conditions described above.

According to a third method, the N-nitroso derivative of the corresponding heterocyclic amines is reacted with dichloroacetyl chloride [see German Patent Specification 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 the appropriate amino alcohol and carbonyl compound with dichloroacetyl chloride under the reaction conditions described above (see M. Businolli: II Farmaco (Pavia) Ed. Sci. 10, 127-134 (1955)). )].

The preparation of the compounds of formula (I) and their effect as an antidote is further illustrated by the following non-limiting examples.

Example 1

Preparation of N-dichloroacetyl-1-oxa-4-azaspiro [4,5] decane (compound 1j

The boiling mixture of 64 g (0.645 mol) of cyclohexanone and 30 g (0.491 mol) of ethanolamine in 100 ml of benzene is continuously removed by distillation. Boiling is continued until 8-8 ml of water is separated. The reaction mixture was then cooled, and 55 g (0.55 mol) of a 40% aqueous sodium hydroxide solution was added, followed by dropwise addition of 74 g (0.5 mol) of dichloroacetyl chloride under external cooling with ice and salts.

The mixture was stirred for an additional two hours at room temperature and then washed with aqueous hydrochloric acid solution and then water.

Benzene is distilled off from the neutral mixture obtained in vacuo. 10 g (0.4 mol) of green crystalline solid are obtained. Recrystallization from absolute ethanol yields a white crystalline product, m.p.

105.5-107 ° C. The structure of the compound can be verified by infrared spectral analysis:

calculated:

% C, 47.63;% N, 5.50; found:

S, 47.12; N, 5.70; Cl, 28.56. Example 2

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

The boiling mixture of 9.8 g (0.1 mol) of cyclohexanone and 7.7 g (0.1 mol) of 2-mercaptoethylamine in 100 ml of benzene is continuously distilled to remove the water formed. Continue boiling until 1.8 ml of water are separated. The reaction mixture was then cooled and 11 g of a 40% aqueous sodium hydroxide solution was added, followed by the dropwise addition of 14.7 g (0.1 mol) of dichloroacetyl chloride from external ice and salt cooling.

The mixture was stirred for another two hours at room temperature and washed with aqueous hydrochloric acid solution and then water. Benzene was distilled off from the obtained neutral mixture in vacuo to give 17.2 g (0.064 mol) of a white powder. Recrystallization from absolute ethanol gave a white crystalline product, m.p. 149-151 ° C. The structure of the title compound can be verified by infrared spectral analysis.

Analysis:

calculated:

44.77% C, 5.22% N, 11.95% S,

26.43% Cl;

found:

44.51% C, 5.31% N, 12.15% S,

26.29% Cl.

Example 3

Preparation of N-dichloroacetyl-8-methyl-1-oxa-4-aza-spiro [4.5] decane (compound 3)

The boiling mixture of 11.2 g (0.1 mol) of 4-methylcyclohexanone and 6.1 g (0.1 mol) of ethanolamine in 100 ml of benzene is continuously distilled to form water. Continue boiling until 1.8 ml of water are separated. The reaction mixture was then cooled, pyridine (8 g, 0.1 mol) was added, followed by the addition of dichloroacetyl chloride (14.7 g, 0.1 mol) under external cooling with ice and salt, followed by the procedure described in Example 2 to give 20.7 g. Recrystallization from absolute ethanol yielded a white crystalline product, m.p. 119-120 [deg.] C. The structure of the compound obtained can be verified by infrared spectral analysis.

Analysis:

calculated:

% C, 49.63;% N, 5.26;

found:

% C, 49.45;% N, 5.35; Example 4

Preparation of N-dichloroacetyl-1-oxa-5-aza-spiro [1,5] undecane (compound 19)

From the boiling mixture of cyclohexanone (17.6 g, 0.18 mol) and 3-aminopropanol (11.2 g, 0.15 mol) in benzene (50 ml), water was continuously removed by distillation. Continue boiling until 2.7 ml of water are separated. The reaction mixture was then cooled, 16 ml (0.165 mol) of a 40% aqueous sodium hydroxide solution was added, and then 22.1 g (0.15 mol) of dichloroacetyl chloride was added dropwise while external cooling with ice and salts was added.

Thereafter, the procedure described in Example 2 was followed to give 15.7 g (0.059 mol) of a greenish white crystalline product. Recrystallization from absolute ethanol gave a white crystalline solid, m.p. 111-112 ° C. The structure of the obtained compound can be verified by infrared spectral analysis.

Analysis:

calculated:

% C, 49.63;% N, 5.26;

found:

% C, 49.52;% N, 5.32;% Cl, 26.45

Preparation of N-dichloroacetyl-1-thia-4-azaspiro [4.4] nonane (compound 10)

From the boiling mixture of 8.4 g (0.1 mol) cyclopentanone and 7.7 g (0.1 mol) 2-mercaptoethylamine in 100 ml benzene, distilled water is continuously removed by distillation. Continue boiling until 1.8 ml of water are separated. 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 while external ice and salt cooling was added.

Thereafter, as described in Example 2, 21.6 g (0.085 mol) of a yellowish oil were obtained, recrystallization from n-hexane to give a white crystalline product, m.p. 83-85 ° C.

The structure of the obtained compound can be verified by infrared spectral analysis.

Analysis:

calculated:

C 42.53, N 5.51, S 12.61,

27.89% Cl;

found:

% C, 42.35;% N, 5.45;

27.56% Cl.

Example 6

Preparation of N-dichloroacetyl-1-thia-4-azaspiro [4.5] decane-1-oxide (compound 12)

13.41 g (0.05 mol) of N-dichloroacetyl-1-thia-4-azaspiro [4.5] decane are dissolved in 100 ml of methylene chloride and a solution of 9.15 g (0.053 mol) of n-chloroperbenzoic acid is added dropwise. in 100 ml of methylene chloride at a temperature between -25 and -15 degrees Celsius. The reaction mixture was then stirred at room temperature for 2 hours and then cooled to 10 ° C. The insoluble material was filtered off and the filtrate was washed twice with 30 ml 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 are obtained, corresponding to a yield of 93%. Recrystallization from absolute ethanol gave a white crystalline product having a melting point of 188 ° C (dec.).

Analysis:

calculated:

H, 5.32; O, 11.26;

4.93% N, 24.95% Cl, 11.28% S;

found:

% C, 42.18;% H, 5.30;% O = 11.35;

N 4.98, Cl 24.90, S 11.30.

The structure of the obtained compound can be verified by infrared spectral analysis.

Example 7

Preparation of N-dichloroacetyl-1-thia-4-azaspiro [4.5] decane-1,1-dioxide (Compound 13)

13.41 g (0.05 mol) of N-dichloroacetyl-1-thia-4-azaspiro [4.5] decane are dissolved in 150 ml of methylene chloride and a solution of 18.12 g (0.105 mol) of m-chloroperbenzoic acid in 200 ml is added dropwise. ml of methylene chloride at a temperature between 0 and 3 ° C. The reaction mixture was then allowed to stir at room temperature for one hour and boiled for another hour.

It is then cooled to 5 ° C, the precipitated solid is filtered off and washed with 50 ml of methylene chloride. The filtrate was washed twice with 50 mm 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 a brown, yellowish crystalline product are obtained, which is then recrystallized from acetone using decolorizing charcoal. The melting point of the white crystalline product obtained is 180-181 ° C (decomposition).

Analysis:

calculated:

H, 5.12; O, 15.99.

N, 4.67; Cl, 23.68; S, 10.68;

found:

40.10 θ / o C, 5.08% H, 16.03% O,

N, 4.70; Cl, 23.60; S, 10.72.

The structure of the obtained compound can be verified by infrared spectral analysis.

All other compounds listed in Table 1, together with their physical characteristics, can be prepared in an analogous manner.

The following are some representatives of herbicides / whose phytotoxicity decreases due to compounds of formula I.

S-ethyl-N, N-dipropylthiocarbamate,

S-propyldipropylthiocarbamate,

S-ethyldiisobutylthiocarbamate,

S-2,3,3-trichlorallyl diisopropylthiocarbamate,

S-ethylcyclohexylethylthiocarbamate,

2-chloro-2 ', 6'-N- (methoxymethyl) acetanilide,

9-ethylhexahydro-1H-azepine-1-carbothiate,

2-chloro-N-isopropylacetanilide,

N, N-diallyl-2-chloroacetamide,

S-4-chlorobenzyldiethylthiocarbamate,

2-chloro-4-ethylamino-6-isopropylamino-symtriazine,

2-chloro-4,6-bis-ethylamino-asymtriazine,

2- (4-chloro-6-ethylamino-symtriazin-2-ylamino) -2-methylpropionitrile,

2-chloro-4-cyclopropylamino-6-isopropylamino-symtriazine, 2,4-dichlorophenoxyacetic acid,

3- (3 ‘, 4‘-dichlorophenyl) -1-methyl-1- (n-butyl) urea,

2-Chloro-2'-ethyl-6'-methyl-N- (1-methyl-2-methoxyethyl) acetanilide,

2-chloro-2 ', 6'-diethyl-N- (1,3-dioxolan-2-ylmethyl) acetanilide,

2-chloro-2 2, 6‘-diethyl-N- (ethoxycarbonylmethyl) acetanilide,

2-chloro-N-ethoxymethyl-2'-methyl-6'-ethylacetanilide,

2-chloro-N- (2'-ethoxyethyl _m j -2 ", 6" -dimethylacetanilid,

2-chloro-N-butoxymethyl-2 ', 6'-diethylacetanilide,

2-chloro-N- (2'-methoxy-1'-methylethyl) -2'-methyl-6-ethylacetanilide,

2-chloro-N-isopropoxymethyl-2 ', 6'-dimethylacetanilide,

Ν, Ν-hexamethylene-S-ethylthiocarbamate,

N- (3-chlorophenyl) -N‘-methyl-N‘-methoxyurea,

N- (3,4-dichlorophenyl) -N‘-methyl-N‘-methoxyurea,

N- (3-chloro-4-bromophenyl) -N‘-methyl-N‘-methoxyurea,

2-butylamino-4-chloro-6-ethylamino-sym-triazine,

2-chloro-4,6-hisisopropylamino-sym-triazine,

2-methylmercapto-4,6-bislsopropylamino-sym-triazine,

2-methylmercapto-4-ethylamino-6-tert-butylamino-sym-triazine,

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

4-amino-6-tert-butyl-3-methylthio-4,5-dihydro-1,2,4-triazin-5-one, 2,4-dichlorophenoxyacetic acid, 2,4-dichlorophenoxypropionic acid, 2, 4-dichlorophenoxybutyric acid, 2-methyl-4-chlorophenoxyacetic acid, 2,4,5-trichlorophenoxyacetic acid, and mixtures of the above compounds.

The dichloroacetamide derivatives of formula (I) may be formulated, alone or together with one or more of the herbicides mentioned above, into solid or liquid formulations by a conventional technique widely used for the production of plant protection products.

For example, the crystalline products of formula I can be converted into wettable powders by the following process:

Wettable powder:

70.0% compound of formula I 17.0% kaolin

8.0% active silicic acid

2.5% sulfonated higher aliphatic alcohol

2.5% sodium salt of ligninsulfonic acid

By mixing the above ingredients in the above proportions in an "Alpine" mill, a composition for use as a wettable powder is readily obtained. When a herbicidally active ingredient is also used, 50% of the herbicide and 20% of the compound of formula I are mixed with the other ingredients.

When the compounds of the formula I are intended for use in reducing the phytotoxicity of known herbicides before sowing, the active ingredients are mixed with the seeds; preferably 20 to 30% by weight of talc is used as carrier.

Some of the compounds of formula I are liquid at room temperature and can therefore be advantageously formulated as emulsifiable concentrates.

A typical emulsifiable concentrate comprises the following components:

Emulsifiable concentrate I:

up to 50% compound of formula I up to 45% solvent (e.g. xylene)% polyoxyethylene alkyl ether emulsifier.

The composition of another emulsifiable concentrate is shown below.

Emulsifiable concentrate II:

% compound 1% EPTC% xylene% polyoxyethylene-alkyl ether emulsifier.

Naturally, also crystalline compounds can be formulated into emulsifiable concentrates. Emulsifiable concentrates are particularly preferred when the phytotoxicity of a liquid herbicide (e.g. EPTC) is to be reduced by a compound of formula I.

Emulsifiable concentrate III:

% 2-chloro-N- (methoxymethyl) -2‘, 6‘-diethylacetanilide% N-dichloroacetyl-1-thia-4-azasplro [4.5] dean% polyoxyalkylacyl emulsifier% xylene

Granulate:

% S-propyl-N, N-diisobutylthiocarbamate

0.5% N-dichloroacetyl-1-oxa-5-azaspiro [5.5] undecane.

94.5% pumice stone.

The compounds of formula I have the effect of an anti-antidote when sprayed together with an inert herbicide - either formulated together or in the form of a spray prepared before use in a mixing container - but processing may also be carried out before spraying with the herbicide. According to a preferred embodiment, the treated seeds are treated with a formulation containing a compound of formula I before sowing and the soil is sprayed with a herbicidal mixture immediately before or after sowing.

The following examples illustrate the effect of compounds of formula I in combination with compounds referred to as Afalon [N- (3,4-dichlorophenyl) -N'-methyl-N'-methoxyurea], Eptam (N, N-dipropyl-S-ethylthiocarbamate) Sencor [4-amino-5-tert-butyl-4,5-dihydro-3-methylthio-1,2,4-triazin-5-one] and Lasso [2-chloro-N- (methoxymethyl) -2 For comparison, known substances of the antidote nature, 1,8-naphthalenic anhydride and N, N-diallyl-2,2-dichloroacetamide, are used to compare phytotoxicity. considers the weight of plants which have only been cultivated using mechanical weed control.

Example 8

The deteriorating effect of Alafon is observed in sunflower culture. The extent of reduction of this adverse effect is also tested when a compound of formula I is also used.

The following four tests are carried out on an area of 20 m ^{2 each} . Afalone 50 WP is used at a rate of 5 kg of active ingredient per hectare. The antidote substance is sprayed onto the area parallel to Afalon in the form of an aqueous suspension.

The results obtained are shown in Table 2 below.

Table 2

 - / * ..... -i ..... 0.5 Dose of antidote substance (kg / ha) 2,0 Raw weight expressed as% relative to the control group 1.0 Afalon 41 41 41 Afalon + 1,8-naphthalenic anhydride 58 69 75 Afalon + N, N-diallyl-2,2-dichloroacetamide 48 51 67 Afalon + compound 2 78 92 95 Afalon + compound 7 67 89 90 Afalon + compound 15 75 93 102 Afalon + compound 17 81 95 99 Control group (mechanically destroyed weeds) 100 ALIGN! 100 ALIGN! 100 ALIGN!

20777S

It is clearly apparent from the determination of the sunflower raw weight that the heterocyclic dichloroacetamides of the invention reduce the phytotoxicity of Afalone significantly better than either 1,8-naphthalenic anhydride or N, N-diallyl-2,2-dichloroacetamide. It is also clear that compound 17 has virtually 100% activity as an antidote.

Example 9

In field trials carried out essentially as described in Example 8, the phytotoxicity of Afalon at 5 kg per hectare was tested on sunflower plants whose seeds were treated with the antioxidant of the invention or known antioxidant before sowing. The results of these tests are compared to those obtained with mechanical weed control (100 percent). It was found that smaller doses of test compounds were found to have the same effect as those of Example 8. The numerical results are shown in Table 3 below.

Table 3

0.25

Afalon 41 1,8-naphthalenic anhydride + Afalon 57 N, N-diallyl-2,2-dichloroacetamide + Afalon 62 Afalon + compound 2 89 Afalon + compound 7 78 Afalon + compound 15 90 Afalon + compound 17 92

Control group (mechanically destroyed weeds)

Dose of an antidote substance (kg / ha)

1,00 0,50

Raw weight expressed as% relative to the control group

41

75

71 75 95 98 86 90 94 96 98 100 ALIGN! 100 ALIGN! 100 ALIGN!

The results do not differ significantly - when measured accurately - from those obtained in Example 1, although smaller doses of antidote compounds were used.

Example 10

The deteriorating effect of Eptane is observed in maize cultures. The extent of the reduction of this undesirable effect is also tested with the compounds of the invention.

The following four tests are carried out on an area of 20 m ^{2 each} . The maize under examination belongs to the hybrid variety 'Beke 270'. Prior to sowing, 13 liters per hectare of liquid herbicide Eptam 6 E and various doses of the antidote-like substance were sprayed onto the surfaces as a tank mixture. The results are shown in Table 4 below.

Table 4

....... 0.5 Dose of an antidote substance (kg / ha) 1.0 Raw weight expressed as% relative to the control group 2,0 Eptam 48 48 48 Eptam + 1,8-naphthalenic anhydride 60 64 70 Eptam4-N, N-diallyl-2,2- chloracetamide 69 84 92 Eptam + Compound 1 98 102 105 Eptam 4-compound 2 90 98 99 Eptam 4-compound 3 94 97 100 ALIGN! Eptam 4-compound 7 97 100 ALIGN! 100 ALIGN! Eptam 4-compound 9 92 97 98 Eptam 4-compound 17 98 100 ALIGN! 100 ALIGN! Eptam + compound 19 96 98 102 Control group (mechanically destroyed weeds) 100 ALIGN! 100 ALIGN! 100 ALIGN!

From the above results, it is clear that five of the seven heterocyclic dichloroacetamides tested eliminate phytotoxic- is described in Example 10, except that the seeds are treated with different doses of the antidote agent before they are seeded again. effect caused by Eptam, but also to the soil treated with 13 liters per hectare of ka- The two compounds have at least the same activity. Eptam 6 E. dumbbells such as Ν, Ν-dichloroacetamide ( [Ardicane j by adjusting the raw weight Plants are introduced- widely used for this purpose. Table 5. Example 1 1 The field tests are performed essentially as Table 5 Dose (kg / 100 kg seeds) 0.25 0.50 1.00 Raw weight expressed - Λ ·· in% - relative to controls- group Eptam 48 48 48 1,8-Naphthalenic anhydride 4- Eptam 68 70 72 N, N-diallyl-2,2-dichloroacetate amid4- Eptam 69 75 80 Eptam -j- compound 1 98 100 ALIGN! 100 ALIGN! Eptam 4-compound 2 95 97 97 Eptam 4-compound 3 97 98 102 Eptam 4-compound 7 98 102 105 Eptam 4-compound 9 90 95 95 Eptam + Compound 17 95 98 98 Eptam 4-compound 19 97 100 ALIGN! 103 Control group (mechanically destroyed weeds) 100 ALIGN! 100 ALIGN! 100 ALIGN!

1S

From the results shown in Table 5, it is apparent that, although smaller doses of antidote agents were used, compounds 1, 3, 7 and 19 practically eliminated the worsening effect of Eptam.

Example 12

The effect of the compounds of the general formula

Sencor 17 Sencor + 1,8-naphthalenic anhydride 30 Sencor + N, N-diallyl-2,2-dichloroacetamide 20 May Sencor + Compound 1 42 Sencor + Compound 7 48 Sencor + Compound 8 45 Sencor + Compound 17 48 Control group (mechanically destroyed weeds) 100 ALIGN!

Even on the phytotoxic effect of Sencor in soybean crops. Immediately after sowing, the soy is treated with a suspension containing 1.5 kg per hectare of Sencor and various doses of an antidote. The results are shown in Table 6 below.

Table 6

Dose of an antidote substance (kg / ha)

0.5 1.0 2.0

Raw weight expressed as% relative to the control group

17 17 41 52 21 26 65 72 70 76 68 76 71 82 100 ALIGN! 100 ALIGN!

From the above results, it is clear that the compounds of formula I have a significantly better anti-antidote effect than either 1,8-naphthalenic anhydride or N, N-diallyldichloroacetamide.

Example 13

Subsequent tests are performed essentially as Tabuika 7. and! Dose (kg / 100 kg seeds)

0.25

Sencor 17 Sencor + 1,8-naphthalenic anhydride 51 Sencor + N, N-diallyl-2,2-dichloroacetamide 26 Sencor + Compound 1 52 Sencor + Compound 7 58 Sencor + Compound 8 55 Sencor + Compound 17 61 Control group (mechanically destroyed weeds) i '/ V- 100 ALIGN!

as described in Example 12, except that soybean seeds are treated with an antidote and Sencor is sprayed onto the soil immediately after sowing at a rate of 1.5 kg per hectare.

The results are shown in Table 7 below.

0.50 1.00

Raw weight expressed as T in% relative to the control group

17 17 64 70 28 51 75 80 79 87 75 82 82 92 100 ALIGN! 100 ALIGN!

207773

The above results illustrate that on soybean pretreated with compounds of formula I, and in particular with compound 17, Sencor practically has no harmful effect, whereas 1,8-naphthalenic acids and N, N-diallyl-2,2-dichloroacetamide have a much weaker anti-antidote effect. .

Example 14

The tests are carried out to determine the phytotoxic effect of Lasso, a formulation containing 2-chloro-N- (methoxymethyl) -2-, 6'-diethylacetanilide as an active substance, in sorghum cultures and to determine how this adverse effect is affected by the addition of compounds of formula I.

The following four field tests are carried out on 20 m ^{2 each} with 4.5 liters per hectare of Lasso 48 EC.

Wettable powder mixtures containing the compound of formula I as an active ingredient are suspended in water and then mixed with an aqueous emulsion of Lasso 48 EC in amounts corresponding to the dosages listed in Table 8 below. The resulting mixture is then applied to the soil after sowing the sorghum but before emergence (pre-emergence treatment). The results were evaluated by comparing the green weight of four week old plants compared to the control group where the treatment was performed by mechanical weed control.

0.5

Table 8

Dose of active ingredient (kg / ha)

1,0 2,0

Raw weight expressed as% relative to the control group

Lasso 48 EC 37

Lasso 48 EC + 1,8-naphthalenic anhydride 61

Lasso 48 EC + N, N-diallyl-2,2-dichloroacetanilide 72

Lasso 48 EC + compound 1 95

Lasso 48 EC-Compound 2 80

Lasso 48 EC + compound 7 90

Lasso 48 EC + Compound 12 75

Lasso 48 EC + Compound 13 92

Lasso 48 EC + compound 14 90

Control group (mechanically destroyed weeds)

37 37 65 70

78 82 97 102 87 92 95 98 78 83 98 100 ALIGN! 96 98 00 100 ALIGN!

Example 1 5

The field tests are carried out essentially as described in Example 10, except that the seeds are treated with different doses of the antidote of the general formula I before sowing and after sowing the area is applied at a rate of 4.5 liters per hectare of Lasso 48 EC. The results obtained by determining the raw weight of the four week old plants and expressed as a% relative to the control group are shown in Table 9 below.

Table 9

Treatment

0.25

Dose of active ingredient (kg / 100 kg seeds)

0.50 1.0

Raw weight expressed as% relative to the control group

Lasso 48 EC 37

Lasso 48 EC + 1,8-naphthalenic anhydride 68

Lasso 48 EC + N, N-diallyl-2,2-dichloroacetamide 75

Lasso 48 EC + compound 98

Lasso 48 EC + compound 2 95

Lasso 48 EC + compound 7 97

Lasso 48 EC + Compound 12 93

Lasso 48 EC + Compound 13 94

Lasso 48 EC + Compound 14 87

Control group (mechanically destroyed weeds)

37 37 71 73

80 85 105 110 98 96 102 105 96 96 98 107 91 85 100 ALIGN! 100 ALIGN!

In conclusion, the test compounds of formula (I) significantly reduced or eliminated the phytotoxic effect of Lasso 48 EC on sorghum plants without exception. In some cases, such as compounds 1, 7 and 13, some stimulating effect was also observed.

The phytotoxicity of the herbicide Eptam SE (containing 75% S-ethyl-N, N-dipropylthiolcarbamate as active substance) on maize was tested in the presence of 0.1% and 50% of N-dichloroacetyl-1-oxa-4-aza-spiro [4, 5] of the dean as an antidote according to the invention. Its amount is based on the amount of active ingredient.

Eptam SE was used at twice the usual dose, i.e. at a rate of 13 liters / ha, corresponding to 9.75 kg / ha of S-ethyl-N, N-dipropylthiolcarbamate. The antidote was used accordingly at 9.75 g / ha (0.1%) and 4.875 kg / ha (50%). Tests were performed on five treated pots, with five untreated pots used as controls. Eptam SE activity alone and in combination with 0.1% and 50% of said antidote was observed. The tests were performed as follows:

The pots with a diameter of 16 cm were filled with slightly sandy soil up to 5 cm from the edge. The soil was compacted and 10 grains of PX-20 maize were sown in each pot. A 5 cm thick layer of treated or untreated soil was then added to the pot top.

The soil was treated as follows: 5 liters of slightly sandy soil were placed in a suitable mixer and 10 g / ha of N-dichloroacetyl-1-oxa-4-aza-spiro [4.5 J decane in alcohol (from an alcoholic solution containing 0.1 mg / ml is used 1 ml into the soil) and then 13 liters / ha of an aqueous emulsion corresponding to the mixture of Eptam SE (1.3 ml of Eptam SE is emulsified with 3 ml of water and the emulsion obtained is applied to the soil). Stirring is continued for a short period of time and then the seeds are immediately covered with treated soil in a 5 cm layer.

The above treatment was repeated by dissolving 49 mg of N-dichloroacetyl-1-oxa-4-aza-spiro 4,5] decane in 2 ml of alcohol and treating the soil with the obtained solution before treatment with Eptam SE. Another experiment was performed using Eptam SE alone.

In the untreated control, corn grains were coated with a 5 cm thick untreated soil layer.

The pots were then kept in the greenhouse for 4 weeks with occasional spraying.

After 4 weeks the plants sprouted from the soil surface and were weighed separately for each pot. The results below correspond to the average of five replicates. The green mass weights are expressed as a percentage of the green mass mass of the untreated control plants. The following results were obtained:

Treatment (active substances)

Dose of active substance, kg / ha

Green mass in% of untreated control

S-ethyl-N, N-dipropylthiocarbamate 9.75

S-ethyl-N, N-dipropylthiocarbamate + N-dichloro-9,75 + acetyl-1-oxa-4-aza-splro [4,5] dean +0,01

S-ethyl-N, N-dipropylthiocarbamate 9,75 + + N-dichloroacetyl-1-oxa-4-aza-spiro [4,5] dean +4,9 control

108

100 ALIGN!

The above results clearly demonstrate that the antidote of the invention is effective even at concentrations as low as 0.1%. When used at a concentration of 50%, it gives full protection to the antidote and also speeds up the growth of corn.

Claims (1)

I will invent the subject A selective herbicidal composition comprising as active ingredient at least one herbicidal compound selected from the group consisting of thiocarbamate, triazine, chloroacetanilide, carbamide or phenoxyacetic acid, in admixture with 0.1 to 50% by weight of a dicliloroacetamide derivative of the formula I (CHA, / \ CH CH _t i, N-C ~  cuct 11 O of. (1) in which X is an oxygen or sulfur atom, or an SO or SO 2 group, n is zero or 1 a R1 and Ra are each hydrogen, C1-C4 alkyl or phenyl substituted with halogen, hydroxy or nitro, or R 1 and R 2 together form a butylene, pentylene or hexylene group, optionally substituted with one or two methyl groups, provided that when n is zero, R 1 and R 2 are other than hydrogen, C 1 -C 4 alkyl or substituted phenyl.