CS258134B2 - Herbicidal agent - Google Patents

Abstract

The herbicidal composition contains as herbicidally active substance 5 to 90% by weight of a thiolcarbamate of the formula III, where R4 and R5 are C1-6alkyl, C3-8cycloalkyl or together hexamethylene, R6 C1-5alkyl, and 0.4 to 26% by weight of an antidote active substance of the formula I, where R1 and R2 are hydrogen, C1-10alkyl, C2-10alkenyl, C5- or C6cycloalkyl, phenyl optionally substituted with C1-3alkyl or halogen or together hexamethylene, and when R1 is hydrogen, R2 has a meaning other than optionally substituted phenyl, R3 is C1-5alkyl or C2-alkenyl. The herbicidal composition has a reduced phytotoxic effect on cultivated plants.

Description

This invention relates to a herbicidal composition comprising a thiolcarbamate as a herbicidally active substance together with an antidote active substance represented by N-(dichloroacetyl)glycinamides.

The new N-(dichloroacetyl)glycinamides have the general formula I

R ¹ Cl \ Z

N—C—CHz—N—C—CH

From II I II \

R2 OR ³ O Cl (I) where

R ¹ and R ² independently represent a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, a cycloalkyl group with 5 or 6 carbon atoms, a phenyl group, a phenyl group substituted once or twice with an alkyl group with 1 to 3 carbon atoms, a halophenyl group or together a hexamethylene group, and when R ¹ is a hydrogen atom, R ² has a meaning other than phenyl or substituted phenyl,

R ³ represents an alkyl group with 1 to 5 carbon atoms or an alkenyl group with 2 to 5 carbon atoms.

Thiolcarbamate compounds of the general formula III have long been widely used in plant protection against undesirable weeds, especially monocotyledonous weeds.

R ⁴ \

N—C—S—R ⁶

R ⁵ O (ΠΙ) where

R ⁴ and R ⁵ independently represent an alkyl group with 1 to 6 carbon atoms, a cycloalkyl group with 3 to 8 carbon atoms or together a hexamethylene group forming a ring with the adjacent nitrogen atom,

R ⁶ represents an alkyl group having 1 to 5 carbon atoms.

Of these thiolcarbamates, the following compounds are most commonly used in practice:

N,N-diisobutyl-S-ethylthiolcarbamate (Butylate),

N,N-di-(n-propyl)-S-ethylthiocarbamate (EPTC),

N,N-di-(n-propyl)-S-(n-propyl) thiolcarbamate (Vernolate),

N,N-diethyl-S-ethylthiolcarbamate (Ethiolate), N-ethyl-N-butyl-S-ethylthiolcarbamate (Pebulat j,

N-ethyl-N-cyclohexyl-S-ethylthiocarbamate (Cycloate) a

N,N-hexamethylene-S-ethylthiolcarbamate (Molinat).

Thiolcarbamate compounds of the general formula III, when used in the amount required to destroy monocotyledonous weeds, also damage protected crops. These phytotoxic properties limit the possibilities of use, or allow use only in doses that do not harm crops and thus reduce the effectiveness of these herbicidal substances.

About twenty years ago, Hoffmann discovered that there are compounds (derivatives of 1,8-naphthoic anhydride) that reduce this phytotoxic effect and, when used together with herbicidally active substances, compensate for their toxic effect on cultivated plants. Compounds with such an effect are called antidotes, or substances with the opposite effect or antidote, i.e. antitoxic substances.

Since then, numerous other such compounds have been discovered and patented, acting as antidotes. Hungarian Patent No. 168,977 describes oxazolidine and thiazolidine derivatives as antidotes; Hungarian Patent No. 170,214 recommends substances based on thiazolidine sulfoxide and thiazolidine sulfone as antidotes. Sulfides are used as antidotes according to Hungarian Patent No. 173,755. Oxazolidine derivatives are also recommended as antidotes in Hungarian Patent No. 176,867. Hungarian Patent No. 179,643 describes N-(benzoylsulfonyl)carbamates, Hungarian Patent No. 180,069 describes N-(benzoylsulfonyl)thiacarbamate, and Hungarian Patent No. 180,068 describes 2,3-dibromopropionamide derivatives as antidotes.

Antidotes based on dichloroacetamide compounds are described in Hungarian patent documents Nos. 176,458 and 176,784. Hungarian patent documents Nos. 176,669, 176,796, 178,892, 178,883, 178,985, 179,092 and 179,093 describe the action of dicarboxylic acid derivatives as antidotes.

The large number of antidotes known from the state of the art, however, proves that despite diligent research, it has not yet been possible to find a compound by which cultivated plants could be protected from the harmful effects of individual herbicidally active substances. Relative evidence of the failure to solve this problem is also that there is no unified opinion on the biochemical processes taking place when adding antidotes and on the mechanism of action of such compounds in the plant organism. The harmful effects of herbicidally active substances are also influenced in various ways by factors acting in parallel (such as temperature, soil moisture, soil pH value) and by the physical properties of herbicidal agents (for example, vapor pressure, solubility in water).

It has now been found that the new N-substituted or N'-substituted N-(dichloroacetyl)glycinamides of the general formula I compensate for the phytotoxic action of the herbicidally active substances of the general formula III.

288134

The subject of the present invention is a herbicidal composition which contains 5 to 90% by weight of a thiolcarbamate of the general formula III

R ⁴ \

NC—S—R ⁶

From II

R ⁵ o (III) where R ⁴ , R ⁵ and R ⁶ have the above meaning, and 0.4 to 26 parts by weight of antivenom active substance of the general formula I,

R ¹ Cl \ /

N—C—CHž—N--C—CH

From II I il \

R ² OR ³ O Cl (I) where R ¹ , R ² and R ³ have the above meaning.

The method for producing antivenom-active compounds, i.e. N-substituted or N'-substituted N-(dichloroacetyl)glycinamides of the general formula I, where R ¹ , R ² and R ³ have the above-mentioned meaning, consists in reacting N-substituted or N'-substituted glycinamide of the general formula II

Rl \

N—C—CH2—NH—R ³

From II

R ² O (II) where R ¹ , R ² and R ³ have the above-mentioned meaning, in the presence of an acid acceptor and optionally in the presence of a solvent, with dichloroacetyl chloride.

The method of producing antivenom-active substances is the subject of our Czechoslovak patent No. AO 217 938. This patent also provides detailed information on the conditions used in the production of such antivenom-active substances, as well as a number of specific examples of the method.

The herbicidal compositions according to the invention are preferably in the form of emulsion concentrates, wettable powders, granules, aqueous or oily suspensions. The preparation of herbicidal compositions containing the antidote according to the invention is illustrated by the following examples, which do not limit the invention in any way.

Example 1

0.5 parts by weight of the active ingredient, a compound of the general formula I, where R1 is phenyl, ^R2 is hydrogen and ^R3 is allyl (mp 109 to 111.5 °C), is dissolved in a mixture of 8 parts by weight of xylene and 3.5 parts by weight of dichloromethane. To this solution are added 80 parts by weight of the herbicidally active ingredient EPTC [N,N-dl-(n-propyl)-S-ethylthiolcarbamate] and 8 parts by weight of an emulsifier mixture consisting of the calcium salt of dodecylbenzenesulfonic acid and alkylphenol polyglycol ether. The solution is homogenized for 15 minutes and then filtered. The emulsion concentrate contains 80.5% by weight of the active ingredient. It is stable after two hours, and shows minimal reversible changes after 24 hours.

Example 2

2 parts by weight of the active ingredient, a compound of the general formula I, where R ¹ and R ² denote ethyl and R ³ is allyl (mp 93 to 95.5 ° Celsius), are dissolved in a mixture consisting of 7 parts by weight of dimethylformamide. 78 parts by weight of the herbicidally active ingredient N,N-diisobutyl-S-ethylthiocarbamate and 6 parts by weight of a mixture consisting of the calcium salt of dodecylbenzenesulfonic acid and alkylphenol polyglycol ether are added to the solution. The mixture is homogenized for 20 minutes and then filtered. The emulsion concentrate contains 80% by weight of the active ingredient. The emulsion is stable after two hours, after 24 hours it shows minimal reversible changes.

Example 3

20 parts by weight of the active substance, a compound of the general formula I, where R ¹ and R ² denote allyl and R ³ is methyl (mp 81 to 82.5 °C), are dissolved in a mixture consisting of 6 parts by weight of xylene and 6 parts by weight of the isoform. 60 parts by weight of Vernolate [N,N-di-(n-propyl)-S-(n-propyl)thiolcarbamate] and 8 parts by weight of an emulsifier mixture consisting of the calcium salt of dodecylbenzenesulfonic acid and alkylphenolpolyglycol ether are added to this solution. After homogenization, the solution is filtered. The emulsion concentrate contains 80% by weight of the active substance. After two hours, the product is unchanged, after 24 hours it shows minimal reversible changes.

Example 4

0.4% by weight of the compound of the general formula I, where R ¹ and R ³ denote allyl and R ² is hydrogen (n _D ²⁰ = 1.525 0) (hereinafter referred to as active ingredient A), is dissolved in 13.6 parts by weight of kerosene. 80% by weight of the herbicidally active ingredient EPTC and 6 parts by weight of an emulsifier mixture consisting of Evemul A and Evemul B are added to the solution. The mixture is homogenized in a laboratory mixer for 15 minutes and then filtered through a folded filter. The emulsion concentrate contains 80.4% by weight of the active ingredient.

Example 5

The procedure is the same as described in Example 4, but instead of 80 parts by weight of EPTC, 80 parts by weight of Vernolate are used.

Example 6

The procedure is the same as described in Example 4, but 80 parts by weight of Butylate is used as the herbicidally active substance.

Example 7

0.9 parts by weight of active ingredient A is dissolved in 3.1 parts by weight of kerosene. 90 parts by weight of EPTC and 6 parts by weight of a mixture of emulsifiers Evemul A and Evemul B are added to the solution. The solution is then stirred for 15 minutes and then filtered through a folded filter. The emulsion concentrate obtained has an active ingredient content of 90.9% by weight.

Example 8

The procedure is the same as described in Example 7, but 90 parts by weight of Vernolate is used as the herbicidally active substance. Example 9

The procedure is the same as described in Example 7, but 90 parts by weight of Butylate is used as the herbicidally active substance.

Example 10

1.6 parts by weight of active ingredient A are dissolved in 12.4 parts by weight of xylene. 80 parts by weight of EPCT and 6 parts by weight of an emulsifier mixture consisting of Evemul A and Evemul B are added to the solution. The solution is stirred for 15 minutes and then filtered. The emulsion concentrate obtained has an active ingredient content of 81.6% by weight. Example 11

The procedure is the same as described in Example 10, but 80 parts by weight of Vernolate is used as the herbicidally active substance.

Example 12

The procedure is the same as described in Example 10, but 80 parts by weight of Butylate is used as the herbicidally active substance. Example 13

3 parts by weight of active ingredient A are dissolved in 16 parts by weight of xylene. A solution of 75 parts by weight of EPTC and 6 parts by weight of a mixture of Evemul A and Evemul B is added while stirring. The mixture is homogenized for 15 to 20 minutes and then filtered.

The emulsion concentrate contains 78% by weight of the active ingredient.

Example 14

The procedure is the same as described in Example 13, but 75 parts by weight of Vernolate is used as the herbicidally active substance.

Example 15

The procedure is the same as described in Example 13, but 75 parts by weight of Butylate is used as the herbicidally active substance.

Example 16

6 parts by weight of active ingredient A are dissolved in a mixture consisting of 6.5 parts by weight of xylene and 6.5 parts by weight of methylene chloride. A solution of 75 parts by weight of EPTC and 6 parts by weight of a mixture of Evemul A and Evemul B are added while stirring. The solution is homogenized and then filtered. The emulsion concentrate contains 81% by weight of active ingredients.

Example 17

The procedure is the same as described in Example 16, but 75 parts by weight of Vernolate is used as the herbicidally active substance.

Example 18

The procedure is the same as described in Example 16, but 75 parts by weight of Butylate is used as the herbicidally active substance. Example 19

11.2 parts by weight of active ingredient A are dissolved in a mixture consisting of 5.4 parts by weight of xylene and 5.4 parts by weight of methylene chloride. 70 parts by weight of EPTC and 8 parts by weight of an emulsifier mixture consisting of Evemul A and Evemul B are added to the solution. The solution is stirred for 15 minutes and then filtered through a pleated filter. The emulsion concentrate contains 81.2% by weight of active ingredients.

Example 20

The procedure is the same as described in Example 19, but 70 parts by weight of Vernolate is used as the herbicidally active substance.

Example 21

The procedure is the same as described in example 238134

10' of ice 19, however, 70 parts by weight of Butylate is used as the herbicidally active substance.

Example 22

19.2 parts by weight of active ingredient A are dissolved in a mixture consisting of 6.4 parts by weight of xylene and 6.4 parts by weight of isoform. 60 parts by weight of EPTC and 8 parts by weight of an emulsifier mixture of Evemul A and Evemul B are added to the solution while stirring. The mixture is stirred for a further 15 to 20 minutes and then filtered. The emulsion concentrate contains 79.2% by weight of active ingredients.

Example 22

The procedure is the same as described in Example 22, but 60 parts by weight of Vernolate is used as the herbicidally active substance.

Example 24

The procedure is the same as described in Example 22, but 60 parts by weight of Butylate is used as the herbicidally active substance.

Example 25

25.6 parts by weight of active ingredient A are dissolved in a mixture consisting of 14.4 parts by weight of xylene and 10 parts by weight of dimethylformamide. 40 parts by weight of EPTC and 10 parts by weight of an emulsifier mixture consisting of Evemul A and Evemul B are added to the solution. The solution is homogenized by stirring and then filtered. The emulsion concentrate contains 65.6% by weight of active ingredients.

Example 26

The procedure is the same as described in Example 25, but 40 parts by weight of Vernolate is used as the herbicidal agent.

Example 27

The procedure is the same as described in Example 25, but 40 parts by weight of Butylate is used as the herbicidally active substance.

Example 28

25 parts by weight of active ingredient A are dissolved in 64 parts by weight of kerosene. 5 parts by weight of EPTC and 6 parts by weight of a mixture consisting of Evemul A and Evemul B are added to the solution. The solution is stirred for 15 minutes and then filtered through a pleated filter. The emulsion concentrate contains 30% by weight of active ingredient.

Example 29

0.4 parts by weight of the active ingredient, a compound of the general formula I, where R ¹ is phenyl, R ^z is ethyl and R ³ is sec-butyl (n _n ²⁰ equals 1.537 3), is dissolved in 4.6 parts by weight of xylene. 90 parts by weight of EPTC and 6 parts by weight of a mixture of Evemul A and Evemul B are added to the solution with stirring. The mixture is stirred for 15 to 20 minutes and then filtered. The emulsion concentrate contains 5% by weight of the active ingredient.

Example 30

0.5 parts by weight of the active ingredient, a compound of the general formula I, where R ¹ is phenyl, R ² is methyl and R ³ is isopropyl (mp = 101 to 102 °C), is dissolved in a solvent mixture consisting of 62 parts by weight of xylene and 26 parts by weight of dichloromethane. 5 parts by weight of Ethiolate (N,N-diethyl-S-ethylthiolcarbamate), 4 parts by weight of Tensiofix AS and 2 parts by weight of Tensiofix IS are dissolved while stirring. The mixture is stirred for 15 minutes in a laboratory mixer and then filtered through a folded filter. The emulsion concentrate contains 5.5% by weight of the active ingredient.

In the above examples, the following emulsifiers are used:

Evemul A: a mixture of alkyl polyglycol ether and alkyl aryl sulfonate,

Evemul B: a mixture of alkylaryl polyglycol ether and alkylaryl sulfonate.

It has now been found that the compounds of the general formula I protect maize in particular against the harmful effects of the thiolcarbamates of the general formula III. Tests carried out to clarify the relationship between dose size and effect have shown that the compounds of the general formula I significantly improve the effect at doses of 0.5 to 64% (based on the herbicidally active substance used, considered as 100%). The following examples describe the biological effect.

Example 31

Test series are carried out in growing containers with an area of 1.13 dm ² , each repeated four times. The boxes are filled with 400 g of air-dried meadow soil, sieved through a 2 mm mesh, with a humus content of 1.4% and a pH value of 7.5. (Soil according to Arana: 61). The test plants are sown in these boxes: maize MVTC 596 (Zea mays), 15 grains per box; green foxtail (Setaria viritis) 0.5 g per box. Then the seeds are covered with 200 g of soil and finally treated chemically by spraying. The amount of chemical spray used is converted into a hectare. 20 ml of water is used to prepare the spray suspension.

After chemical treatment, 100 g of soil is added to the boxes and they are watered up to 65% of their water intake capacity. Constant humidity is maintained by daily watering during the growing period.

It is irradiated daily for 14 hours using a high-pressure mercury lamp (HgMI/D 400 Wj). The average daily temperature is maintained at 25 °C (minimum 23 °C, maximum 27 °C). Untreated controls are used for the evaluation of the tests.

In order to allow comparison with known antidotes, the widely used compound R-25 788 (N,N-diallyl-2,2-dichloroacetamide) is used as a reference substance. The evaluation is carried out on the tenth day after treatment by measuring the length of the shoots and evaluating morphological changes.

The following rating scale is used to assess morphological changes:

100% healthy corn % slight leaf curl, slight deforce % moderate stem curl, moderate leaf deformation % perfect deformation, cessation of plant growth and cessation of plant development.

Green grass used as a monocotyledonous sown weed is always destroyed by the action of a herbicide in the presence of an antidote, meaning that it is not affected by the protective action of the antidote active substance of general formula I.

The shoot lengths and plant appearance are always given in Table I in comparison with untreated control plants. The treatment is carried out with EPTC at a rate of 5.6 l/ha, with either 8% or 16% of the respective antidote active ingredient being added to the herbicidal composition.

TABLE I

Compound treatment T. t. (°C) or n _D ²⁰ Shoot length, % Appearance of corn, expressed in % R ¹ R ² R ³ 8% 16% 8% 16% EPTC 72 EC EPTC + R25788 Phenyl ethyl methyl 99 to 100 35 95 a, b 56 b 78 points 50 98 a, b 70 b 80 points phenyl ethyl ethyl 56 to 58 49 points 69 points 65 points 80 points phenyl ethyl n-propyl 94 to 95.5 33 37 55 55 phenyl ethyl iso-propyl 109 to 29 29 55 55 phenyl ethyl allyl 110.5 83 to 86 45 58 points 65 points 70 points phenyl ethyl n-butyl 1,525 6 29 36 50 50 phenyl ethyl sec-butyl 1,537 3 31 24 55 50 phenyl ethyl iso-butyl 118 to 29 29 50 55 phenyl ethyl tert-butyl 119.5 100 to 101 31 29 50 55 allyl allyl methyl 81 to 82.5 38 53 points 60 65 points allyl allyl ethyl 87 to 89.5 39 48 55 60 allyl allyl allyl 50 to 51 34 66 points 63 points 50 ethyl ethyl allyl 93 to 95.5 85 points 93 a, b 85 points 99 a, b iso-butyl iso-butyl ethyl 75 to 76.5 33 48 55 65 points methyl methyl n-propyl 76 to 79 33 44 50 57 methyl methyl iso-propyl 98.5 to 100 27 30 52 53 methyl methyl allyl 105 to 112 37 32 55 80 points methyl methyl ethyl 101.5 to 32 40 55 54 ethyl ethyl n-propyl 103 49 to 52 80 points 80 points 88 points 88 a, b ethyl ethyl iso-propyl 89 to 92 53 points 58 points 69 points 55 ethyl ethyl ethyl 112 to 25 36 53 65 points cyclohexyl ethyl ethyl 113.5 86—88.5 29 21 50 55 phenyl hydrogen ethyl 128.5—131 81 points 83 points 86 points 92 a, b allyl hydrogen allyl 1,525 0 92 a, b 100 a, b 100 a, b 66 b 99 a, b 76 b n-propyl n-propyl allyl 52—54 46 points 65 points cyclohexyl hydrogen allyl 1,519 8 77 points 94 a, b 92 a, b 99 a, b phenyl hydrogen allyl 109—111.5 76 points 92 a, b 80 points 99 a, b 2,6-dimethyl- phenyl hydrogen ethyl 1,529 0 55 points 54 points 64 points 69 points 2,6-diethyl- phenyl hydrogen ethyl 1,525 2 52 points . 60 points 64 points 64 points 3-chlorophenyl hexamethylene H ethyl ethyl 1522 9 1.5317 38 42 48 38 56 64 points 69 b 50

Compound treatment T. t. (°C) Shoot length, % Corn appearance, or n _D ²⁰ expressed in %

R ¹ R ² R ³ 8% 16% 8% 16% ethyl ethyl n-butyl 65—66 42 42 57 59 ethyl ethyl iso-butyl 59.5—62.5 38 45 50 54 ethyl ethyl sec-butyl 93—94 31 30 52 53 ethyl ethyl tert-butyl 128—129 33 29 50 50 phenyl methyl ethyl 62 to 66 74 points 77 points 97 a, b 99 a, b 82 b phenyl methyl n-propyl 97 to 98.5 46 points 62 points 55 phenyl methyl allyl 102 to 103 60 points 85 points 90 a, b 97 a, b phenyl iso-propyl ethyl 85 to 86 31 28 50 50 phenyl iso-propyl allyl 79 to 82 32 31 50 50 methyl hydrogen methyl 36 to 40 87 points 90 a, b 100 a, b 100 a. b ethyl hydrogen ethyl 79 to 82.5 83 points 81 points 100 a, b 97 a, b n-propyl hydrogen n-propyl 1,501 0 88 points 78 points 98 a, b 99 a, b iso-propyl hydrogen iso-propyl 132 to 133 47 points 48 81 points 87 a, b n-butyl hydrogen n-butyl 1,495 0 57 points 65 points 63 points 55 sec-butyl hydrogen sec-butyl 73 to 76 55 points 41 67 points 57 benzyl hydrogen benzyl 82 to 84 34 40 50 50 n-propyl n-propyl allyl 1,502 0 43 points 75 points 59 94 a, b phenyl methyl metbyl 146 to 147.5 95 and, b 96 a, b 73 points 79 points phenyl 2,6-dimethyl- methyl iso-propyl 101 to 102 40 42 64 points 50 phenyl hydrogen methyl 154 to 155 41 45 61 55 2.6-dimethylphenyl 2.6- diethyl- hydrogen allyl 190 to 192 35 41 50 57 phenyl 2,6-diethyl- hydrogen methyl 158 to 160 30 35 58 51 phenyl hydrogen allyl 118 to 121 31 38 62 points 65 points allyl hydrogen n-butyl 54 to 56 35 36 60 55 allyl hydrogen isobutyl 60 to 63 32 38 64 points 70 points allyl hydrogen iso-propyl 61 to 62.5 56 points 68 points 65 points 75 points allyl hydrogen n-propyl 1,511 2 94 and, b 98 a, b 80 points 100 a, b allyl hydrogen ethyl 80 to 83 95 and, b 89 a, b 88 a, b 100 a, b 10.6 13.3 11.7 13.9

a compared to untreated control no significant differences (with 95% confidence) b compared to EPTC treatment without antivenom significant differences (with 95% confidence).

Example 32

Dose and action

The action of the compound of the general formula I in various doses was investigated using the active ingredient A. The tests were carried out according to the method of example 31, using the emulsions usable by spraying according to examples 4 to 30. For comparison, tests were also carried out with EPTC, Vernolate, Butylate, Ethlolate, as active ingredients of herbicidal compositions without antidote content and tests with herbicidal compositions containing the said herbicidally active ingredients and the known antidote R 25 788. During the evaluation, the length of the shoots was measured and morphological changes were evaluated. The test results are given in the tables below.

The symbols "a" and "b" in the tables always have the following meaning:

and active substance A b antidote R 25 788.

The corn was treated with EPTC at a rate of 5.6 l/ha and with the active ingredient A at the indicated rate, or with the antidote R 25 788.

Antidote

1/ha %

TABLE II

Corn shoot length a b A a—b

Morphological changes a b Δ a-

0.028 0.5 104 83 + 21 98 83 + 15 0.056 1.0 102 85 + 17 97 85 + 12 0.112 2.0 96 98 — 2 98 99 — 1 0.224 4.0 95 98 — 3 98 98 0 0.448 8.0 97 99 — 2 96 100 — 4 0.896 16.0 92 87 + 5 100 95 + 5 1,792 32.0 90 80 + 10 100 97 + 3 2,584 64.0 78 85 — 7 98 95 + 3 sd ₅ % = 16.3% among any sd ₅ % = 13.8% among any

combinations combinations appearances corn treated with EPTC without antidote 63% shoot length corn treated with EPTC without antidote 52%

In a similar manner, Butylate was used in an amount of 6.0 l/ha, then Butylate with active ingredient A or with R 25 788. The results are given in Table III (values in percentages with respect to the untreated control).

TABLE III

Antidote 1/ha % Corn shoot length and Appearance b A a—b and b Δ a—b 0.03 0.5 105 88 + 17 97 85 + 12 0.06 1.0 102 81 + 21 97 84 + 13 0.12 2.0 96 90 + 6 98 97 + 1 0.24 4.0 96 98 — 2 98 100 — 2 0.48 8.0 93 94 — 1 99 99 0 0.96 16.0 81 90 — 9 94 99 — 5 1.92 32.0 82 74 + 8 99 92 + 7 3.84 64.0 82 72 + 10 94 98 — 4 sd ₅ % = 14.5% among any SDs% = 11.7% among any combinations combinations length of corn shoots treated with Butylate corn appearance (with regard to % without antidote controls) treated with Butylate without antidote 77.6% ( with regard to % control) 85% Same test repeated with Vernolate used at a rate of 4.0 1/ha. The results are listed in Table IV. TABLE IV Antidote % Corn shoot length Appearance 1/ha and b A a—b and b A a—b 0.02 0.5 96 84 + 12 97 92 + 5 0.04 1.0 98 86 + 13 100 96 + 4 0.08 2.0 96 92 + 4 100 99 + 1 0.16 4.0 96 104 — 8 99 100 — 1 0.32 8.0 99 95 + 4 98 100 — 2 0.64 16.0 93 87 + 6 100 99 + 1 1.28 32.0 90 88 -1- 2 98 100 - 2 2.56 64.0 90 89 + 1 89 96 — 7

SD ₅ °/ ₀ = 11.5% between any combinations

SDi,% = 12.7% between any combinations shoot length (without antivenom) 76% appearance (without antivenom) %

The same test was repeated with Ethiolate applied at a rate of 8.0 l/ha. The results are shown in Table V.

TABLE V

Antidote % Corn shoot length Appearance

1/ha b a A a—-b a b Δ a—b

0.02 0.25 92 95 + 3 100 100 0 0.04 0.5 102 94 — 8 100 100 0 0.08 1.0 109 102 — 7 100 100 0 0.16 2.0 110 112 + 2 100 100 0 0.32 4.0 96 109 + 13 100 97 +3 0.64 8.0 91 106 + 15 100 100 0 1.28 16.0 89 96 + 7 100 100 0 2.56 32.0 94 96 + 2 100 100 0 5.12 64.0 106 86 — 20 100 100 0 sd ₅ % = 11% among any SD ₅ °/ ₀ = 15% between any

combinations combinations shoot length (without antidote) appearance (without antidote) % 77 %

From the values in the tables it is clear that the active ingredients of the general formula I are particularly advantageous in the dosage range of 0.5 to 2.0% over the known and widely used agent R 25 788. At higher doses no difference between the two antacids was demonstrated in statistical tests. When used in amounts of 4 to 16%, the corn remained healthy, without any symptoms.

The active ingredients of the general formula I promote the selectivity of thiolcarbamates. The phytotoxic action of these compounds is not manifested, while the herbicidal action of these herbicidal compounds remains preserved.

Claims (1)

A plerbicidal composition comprising, as a herbicidally active substance, thiolcarbamates and an antioxidant, characterized in that it contains 5 to 90% by weight of the thiolcarbamate of the general formula III R ⁴ \ N — C — S — R ⁶ Z II R ⁵ O (III) where R ⁴ and R ⁵ are each independently C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, or together are a hexamethylene group forming a adjacent ring nitrogen atom, R ⁶ represents an alkyl group having 1 to 5 carbon atoms, and 0.4 to 26% by weight of an anti-antidote compound of formula I, VYNALEZU R ¹ Cl \ Z N — C — CH2 — N - C — CH Z il I II \ R 2 OR ³ O Cl (I) wherein R ¹ and R ² are each independently hydrogen, C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 5 or C 6 cycloalkyl, phenyl, phenyl mono- or di-substituted alkyl having 1 to 3 carbon atoms, a halophenyl group or together a hexamethylene group, and when R ¹ is a hydrogen atom, R ^{2 has} a meaning other than phenyl or substituted phenyl, R ³ is C 1 -C 5 alkyl or C 2 -C 5 alkenyl.