HERBICIDAL COMPOSITIONS WITH PROLONGED ACTION AND IMPROVED SELECTIVITY

Abstract: A composition for the extension and increase of the activity of herbicidal compositions containing as herbicidally active ingredient at least one carbamate and/or thiolcarbamate and/or chloroacetanilide and/or dichloroacetanilide derivative and optionally antidotes therefor, which comprises at least one thio- or dithiophosphoric acid ester of formula (I), wherein R stands for identical or different alkyl, alkenyl, isoalkyl, isoalkenyl, haloalkyl, haloalkenyl, isohaloalkyl or isohaloalkenyl groups, each containing up to 4 carbon atoms; R' represents identical or different alkyl, alkenyl, isoalkyl, isoalkenyl, haloalkyl, haloalkenyl, isohaloalkyl, isohaloalkenyl groups, each containing up to 4 carbon atoms; X is oxygen or sulfur, X1 is oxygen or sulfur, with the proviso that at least one of the X1 groups is other than oxygen.

Description: ~ > - HERBICIDAL COMPOSITIONS WITH PROLONGED ACTION AND PROVED SELECTIVITY The invention relates to novel herbicidal com¬ positions and to a process for employing these composi¬ tions. More particularly, the invention concerns novel herbicidal compositions comprising thio- or dithiophos¬ phoric acid esters in association with herbicides of the carba ate, thiolcarba ate, chloroacetanilide or dichloro- acetanilide type or any desired combination of two or more of such herbicidally active ingredients and optionally antidotes. The invention further provides a process for the application of these compositions or compositions containing the active ingredients separately. The thio- or dithiophosphoric acid esters em- ployed in the compositions according to the invention are encompassed by the following formula (I) R in which R stands for identical or different alkyl, alkenyl, isoalkyl, isoalkenyl, haloalkyl, halo¬ alkenyl, isohaioalkyl or isohaloalkenyl groups each having up to 4 carbon atoms in the alkyl and alkenyl moieties, respectively; R' represents identical or different alkyl, alkenyl, isoalkyl, isoalkenyl, haloalkyl, halo¬ alkenyl, isohaioalkyl or isohaloalkenyl groups ^ each having up to 4- carbon atoms in the alkyl ali. moieties, respectively; X ts oxygen or sulfur; X-, Is oxygen or sulfur with the proviso that at least one of the X-, substituents is other than oxygen. Compounds of the formula (I), wherein the sub- stituents are as hereinabove defined, can be prepared in a known manner, for example following the reaction illus¬ trated on Chart A. The process is generally carried out under atmospheric pressure, at a temperature between 0 C and 80 C, in a medium inert under the reaction conditions. The starting compounds are known in the art or can be prepared in a known manner. The insecticidal activity of the compounds of formula (I) is known in the art. It has, however, not been disclosed in the prior art that these compounds in¬ crease and extend the activity of carbamate, thiol- carbamate, chloroacetanilide and dichloroacetanilide herbicides. Another newly discovered property of the com¬ pounds of formula (I) is that they increase and extend the activity of antidotes conventionally used in combina¬ tion with thiolcarbamate and chloroacetanilide herbicides. The increase in activity and its duration is achieved without any harmful side-effect on the cultivated plants. Background Art Herbicides of the carbamate, thiolcarbamate, chloroacetanilide and dichloroacetanilide type are widely used in the everyday practice of agriculture. They are for example disclosed in the United States Patent Specifica¬ tions Nos. 2,863,752; 2,8 β 4, β 83; 3,442,945; 2,913,327; 2,695,225; 2,906,614; 3,330,643; 3,330,821; 3,330,642; 3,198,786; 3,573,031 and 3,175,897. As previously stated, herbicides are widely used in the agriculture. The herbicidally active chloro¬ acetanilide and thiolcarbamate derivatives, however, injure the cultivated plants as well, they are therefore often combined with various antidotes. Certain antidotes, which reduce the phytotoxic effect of thiolcarbamate herbicides on agricultural plants show a protecting ef¬ fect in combination with chloroacetanilide herbicides, too, in various cultures, e.g. maize C.J. Robert, C. Levitt, D. Penner: J. Agr. Pood. Che . 27(3), 533-536 (1979)]. Such antidotes are for example disclosed in the Belgian Patent Specifications Nos. 782,120 and 806,038, in the United States Patent Specifications Nos. 3,893,338 and 3,931,313 and in* the Hungarian Patent Specifications Nos. 165,736, 176,784 and 168,977. In addition to their toxic effect on the culti¬ vated plants, another problem in connection with these herbicidally active ingredients is that the duration of their effect is not satisfactory. As it is well known, immediately after spraying the concentration of the above-mentioned herbicides and antidotes is very high in the upper layer of the soil, but la eron it decreases rapidly. This may lead to an invasion of weeds and, as a result, to the injury of cultivated plants. The reasons for this phenomena are discussed by Kaufman, D.D.-Kearney, P.C. (Appl. llicrobiol. 13, 443-446 (1965)) and Pox, J.L. (Science, 225, 1029-1031 (1983)). It is concluded that especially the active ingredients con- taining mN-C__(0) groups are rapidly decomposed by the microbes present in the soil. Detailed description of the invention In our experiments carried out with the aim of extending the duration of the effect of carbamate, thiol¬ carbamate, chloroacetanilide and dichloroacetanilide herbicides, optionally combined with antidotes we have surprisingly found that the thio- and dithiophosphoric acid ester derivatives according to the invention prolong the action of said herbicides, increase their activity and improve their selectivity. In addition, we have found, that the action of the simultaneously used antidotes is also extended and their activity is Increased. By using the thio- and dithiophosphoric acid ester derivatives according to the invention the duration of herbicidal effect can be optimalized, the doses of the herbicides employed can be reduced, their selectivity can be increased, and similar favourable effects can be achieved also when the compounds according to the inven- tion are employed in association with antidotes. By employing the extenders according to the in¬ vention, the herbicidal compositions comprising carbamates, thiolcarbamates, chloroacetanilides and/or dichloroacet- anilides as herbicidally active ingredient and optionally antidotes can be used more advantageously in maize, sun- - _> - -flower, cereals, soya, sugar beet, vegetables and fruits than the hitherto employed compositions containing the above-mentioned active ingredients and optionally anti¬ dotes. The extenders according to the invention are particularly effective in combination with S-ethyl bis- (2-methylpropyl)-carbamothioate, S-ethyl eyelohexylethyl- -carba o hioate, S-(2,3-dichloroallyl)-diisopropylthio- -carbamate, S-ethyl dipropylcarbamothioate, S-ethyl-N,N- -hexamethylene-thiocarba ate, S-propyl-dipropylthiocarba- ate, 2-chloroallyl-diethyl-dithiocarbamate, 1-methyl- ethyl-3-chlorophenylcarbamate, 4-chloro-2-butinyl-3- -chlorophenyl-carbamate, 2-chloro-2,6-diethyl-N-methoxy- methyl-acetanilide, 2-chloro-2-methyl-6-ethyl-N-rr_ethoxy- ethyl-acetanilide, N-butoxymethyl-2-chloro-2,6-diethyl- -acetanilide, N-chloroacetyl-N-(2,6-diethylphenyl)- -glycine, 2-chloro-N-(1,6-dimethylphenyl)-N-(methoxy- ethyl)-acetamide, N-(2-chloroethyl)-2,6-dinitro-N-propyl- -4-(trifluoromethyl)-aniline, 2-chloro-N-(2,6-dime hyl- phenyl)-N-(lH-pyrazol-l-yl-methyl)-acetamide, 2-chloro- -N-(2-ethyl-6-me hylphenyl)-N-(2-methoxy-l-methyle hyl)- -acetamide, 2-chloro-N-(2,6-diethylphenyl)-N-(2-propoxy- ethyl)-ace amide, 2-chloro-N-(l-methylethyl)-N-phe yl- -acetamide and N,N-diallylchloroacetanilide, and op- tionally antidotes. The compositions containing the compounds of formula (I) as extenders in combination with the above- - entioned herbicides and optionally antidotes can be applied to the soil or the plants or incorporated into the soil prior to or after sowing, pre- or postemergently, depending on the properties of the herbicides present in the compositions. Alternatively, the herbicides, antidotes and the compounds according to the invention may be for¬ mulated separately and can be employed simultaneously or subsequently, but the time interval between the applica- - o - tion of the individual components should be mini alized. The dose of the compounds according to the in¬ vention and the mutual proportions of the various com¬ ponents may be varied within a wide range. The actual dose is a function of the chemical and physical properties of the herbicides, the cultivated plants, weeds, type of the soil, climatic factors and further similar conditions which are well known for those skilled in the art. In the combinations according to the invention the ratio of the herbicidally active component to the thio- or dithiophosphoric acid esters of the formula (I) generally is between 30:1 and 1:1, preferably 10:1 and 3:1, most preferably 6:1 and 5:1. The quantity of the thio- or dithiophosphoric acid ester component in the first line depends on the microbial activity of the soil. Generally it is employed in an amount of 0.1 to 8.0 kg, preferably 0.2 to 3-0 kg, most preferably 0.5 to 3-0 kg pro hectare. In the combinations according to the invention the antidotes are generally used in the u≤ual ratios re¬ lated to the herbicides, but lower doses are also possible. The total active ingredient concentration in the compositions according to the invention is 0.1 to 95 % by mass, preferably 1 to 90 by mass. Prom the concentrated compositions according to the invention the ready-to-use formulations are prepared by dilution. The formulations prepared by the admixture of the herbicides, the extenders according to the invention and optionally the antidotes directly prior to applica- tion (e.g. tank mixtures) which are, if desired, diluted, are also within the scope of the invention. The composi¬ tions containing the extender alone generally contain 0.1 to 95 % by mass, preferably 1 to 90 % by mass of active ingredient. The compositions according to the invention may be formulated as solid or liquid preparations conven¬ tionally used in the agriculture, depending on the physi¬ cal and chemical properties of the active ingredien (s). The compositions contain the active ingredient(s) in as- sociation with acceptable, non-phytotoxic solid or liquid carriers and * optionally surfactants. The compositions optionally contain further additives, which have a favourable influence on the ac¬ tivity, e.g. decrease the volatility of the active in- gredients or facilitate the application. Such additives include protecting colloids, thickening agents, adhesives, stabilizators and solid carriers with high adsorption capacity. The compositions according to the invention generally contain in addition to the above-defined amount of active active ingredient( s) 1 to 99 % by mass of solid or liquid carriers and optionally surfactants. As a carrier any non-phy otoxic inorganic or organic material of natural or synthetic origin may be employed. Solid carriers include clays, natural or syn¬ thetic silicates, silicic acid, dolomite, caoline, diatomaceous earth, flour of vegetable products, starch, etc. As a liquid carrier for example water, alcohols, esters, ketones, mineral oil fractions, aromatic, ali- phatic or cyclic hydrocarbons, halogenated hydrocarbons, dimethyl sulfoxide, etc. can be employed. The surface active agents include emulsifying, dispersing and wetting agents, which are of ionic and/or non-ionic character. Typical representatives of surfactans are the salts of ligninesulfonic acid, sal ~ s of phenol- and naphthalinesulfonic acids, polyccndensation product of ethylene oxide with fatty alcohols or fatty acids or fatty acid amides, arlalkylsulfo ates, substituted phen¬ ols, e.g. alkyl- and arlphenols. The solid compositions according ~o the inven- r-.NO 0F« β «* - 3 - tion may be finished as powders, dusking powders, granu¬ lates, etc., while the .liquid formulations include sol¬ utions, emulsifyable concentrates, emulsions, concentrat¬ ed suspensions, wettable powders, sprays or pastes. The concentrated formulations may be diluted as desired, and are prepared in a conventional manner. The compositions according to the invention may be employed simultaneously i^h ether plant protecting agents, e.g. herbicides, pesticides, fungicides, bac- tericides, and plant growth regulators. Generally any plant protecting agent which is compatible with the chloro¬ acetanilide, dichloroacetanilide, carbamate and thiol¬ carbamate herbicides is suitable for simultaneous appli¬ cation. According to the invention the formulations con¬ taining an effective amount of one or more herbicides of the carbamate, thiolcarbamate, chloroacetanilide and di¬ chloroacetanilide type and optionally antidotes in asso¬ ciation with the thio- and dithiophosphoric acid esters of ~he formula (I) are applied to the plants or the soil containing the seeds of the plants. Alternatively, the herbicidally active ingredients and/or the antidotes and/or the extenders according to the invention may be formulated separately, and applied to the plants or to the soil either simultaneously or subsequently. The ac¬ tive ingredients are employed in an effective amount. The formulations are applied to the plants or the soil for example by spraying, dusting, vaporization, etc., using conventional techniques. The invention is elucidated in more detail by the aid of the following non-limiting Examples. Example 1 0-ethyl-5-n-propyl-3-(dl-2-propenylamino )-di- thio hosphoric acid ester "^ 30 g of chloroacetic acid- -(2-propenyl)-amide in 2CC ml of acetonitrile are stirred with 40 g of 0- -e hyl-S-n-propyl-thiophosphoric acid potassium salt at room temperature for 12 hours. After stirring, the re¬ action mixture is refluxed for 3 hours. The salts precipi¬ tated upon cooling are eliminated from the solution, and the solvent is distilled off under reduced pressure. The residue is taken up in 100 ml of methylene chloride and washed with 30 ml of 1 n sodium hydroxide and subsequent¬ ly 30 ml of water. The solvent is then distilled off on a bath of 40 to 50 °C to yield the title compound with a good yield. n^ 3 = 1.5221. Example 2 0,S-di-2-chloroethyl-S-(di-2-propenylamino)-di¬ thiophosphoric acid ester Into a flask equipped with a stirrer, thermo¬ meter and dropping funnel there are added 25.5 g (0.1 mole) of 0,S-di-2-chloroethyl-dithiophosphoric acid, 17.3 g of diallyl-chloroacetamide and 100 ml of benzene. To the mixture 11 g of triethyl amine are slowly added, under vigorous stirring. A rapid reaction takes place, which results in the precipitation of the amine hydrochloride formed. V/hen the addition is complete, the mixture is re- fluxed for 3 to 4 hours. The hydrochloride formed in the theoretical amount is eliminated by filtration. The fil¬ trate is washed with 50 ml of a 20 % sodium hydroxide sol¬ ution and subsequently with water. The solvent is distill- ed off in vacuum, and the title compound is obtained with a good yield. 5 - - 1.5440 Example 3 0,3-diethyl-S-(di-2-propenylamir_3)-dithiophos- > phoric acid ester 18.4 g of 0,3-diethyl-dithio hosphoric acid are dissolved in 50 ml of water, and the solution is neutral¬ ized with 6.8 g of potassium carbonate. In a flask equipp¬ ed with a stirrer, thermometer and dropping funnel 17.3 g of diallyl chloroacetamide in 50 ml of acetone are added to the above solution dropwise, at 20 °C. ' ■Vhen the addition is complete, the mixture is stirred at 45 to 50 °C for 4 to 5 hours, whereupon it is poured into 500 ml of water and the precipitated oily product is separated. The aqueous phase is extracted with benzene twice, dried over sodium sulfate, and the solvent is distilled off. The title compound is obtained with a The following compounds are prepared in an analogeous manner. 1 methyl methyl propenyl propenyl 1.4338 2 n-propyl n-propyl propenyl propenyl 1.5242 3 propenyl propenyl propenyl propenyl 1.5393 4 2-chloro- 2-chloro- 4-propyl 4-propyl e hyl ethyl 1.5282 r ~ D ethyl 3-chloro- propenyl propenyl propyl 1.5065 6 ethyl i-propyl propenyl propenyl 1.5137 7 ethyl ethyl 2-chloro- 2-chlo o- e hyl ethyl 1.5386 3 2-chloro- 2-chlo o- e hyl n-propyl ethyl ethyl 1.5133 9 2-chloro- 2-chloro- n-propyl i-butyl ethyl e hyl 1.5344 10 2-chloro- 3-chlo o- propenyl propenyl ethyl propyl 1.5013 Example 4 In the biological tests the active substances according to Examples 1, 2 and 3 and the compound No. 10 were used in the following manner: 40 parts by weight of active ingredient are dissolved in a mixture of 32 parts by weight of xylene and 22 parts by weight of dichloromethane, and to the sol¬ ution an emulsifying agent containing the mixture of 6 parts by weight of alkylarylsulfonic acid calcium and fatty acid-polyglycol ester is added. The solution is homogenized by stirring and is then filtered. An emulsion concentrate containing 40 % by weight of active ingredient is obtained. Example 5 Examination of the duration of activity and increase in herbicidal effect of chloroacet¬ anilide herbicides when combined with the com¬ pounds of formula (I) Tests were carried out under foil preemergent- ly, in pots of 12 cm diameter, on "chernosiom" brown for¬ est soil containing 1.63 % of humus. The following treatments were performed: 1) control 2) 2-chloro-2' ,6'-diethyl-N-(methoxyτnethyl)-acetanilide 1 kg/ha (Lasso) 3) 2-chloro-2' ,6 , -diethyl-N-(methoxymethyl)-acetanilide 2 kg/ha (Lasso) 4) 0,S-diethyl-S-(di-2-propenylamino )-dithiophosphoric acid ester (product according to Example 3) 200 g/ha 5) 0,S-diethyl-5-(di-2-propenylamino )-di hiophosphoric acid ester (product according to Example 3) 500 g/ha 6) 2-chloro-2' ,6'-diethyl-N-ζmethoiymethyD-acetanilide 1 kg/ha (Lasso) + 0,S-diethyl-3-(di-2-propenylamino )- -dithiophosphoric acid ester (product according to Example 3) 500 g/ha 7) 2-chloro-2' ,6'-diethyl-N-(methoxymethyl)-acetanilide 2 kg/ha (Lasso) -+- 0,3-diethyl-3-(di-2-propenylamino)- -dithiophosphoric acid ester (product according to Example 3) 200 g/ha The compositions were used as a tank mixture and applied to the pots In an amount of 220 lit/ha by spraying. As a test plant maize was used. Into each pot 5 seeds were sown. As a weed wild millet (Panicum ssp) was employed, since of the monocotyledonous weeds grown from seeds wild millet is the most resistant to herbici¬ des. Therefore, this test weed is excellently suitable for evaluation of the efficiency of a herbicidal agent or com¬ bination. Of wild millet 20 seeds were sown into each pot. After spraying, the pots containing the culti¬ vated plants and weeds, respectively were kept at 23 to 30 °C, the soil was calibrated to a water capacity of 70 to 80 % in order to increase the decomposition rate of herbicides. 15 and 30 days after sowing and spraying, the overground vegetable parts were removed and new seeds were sown without substantial admixture of the surface. In this way the activity increasing and herbicide action extend¬ ing properties of the compounds according to the inven¬ tion were tested under "provocative" conditions. Evaluation was carried out on the 15th day. In case of wild millet the killing ratio ( ), in case of maize the phytotoxicity (EWRC scale) were calculated. On the EWRC scale the score 1 means that there is no phyto¬ toxicity, while the score 9 represents total weed killing. Tests were carried out in four repetitions. Effect of the active ingredients on the killing ratio of wild millet (Panicum spp) No . of K Kiilllling in % of the controll on the treatments according to 15 30th 45th Example 5 day 1 0 0 0 2 0 0 0 3 13 0 0 4 0 0 0 5 0 0 0 6 100 100 67 7 100 100 100 The effect of active ingredients on the injury of maize (Zea mays) No. of treat¬ Ph totoxicity (EWRC-scale) on the ments accord¬ 15th 30th 45th ing to day Example 5 1 1 1 1 2 1 1 1 3 1 1 1 4 1 1 1 5 1 1 1 6 1 1 1 7 1 1 1 The test results show that when employed alone both 2-chloro-2' ,6'-N-(methoxymethyl)-acetanilide and the product according to Example 3 (representing the compounds according to the invention) are ineffective against wild millet. But their efficiency has surprisingly been in¬ creased, when the two compositions were employed together. While a 2 kg/ha dose of 2-chloro-2' ,6'-diethyl-N-(methoxy- methyl)-acetanilide showed a slight effect against wild millet on the 15th day only, the rest combinations re¬ sulted In a 67 to 100 % killing of wild millet even ac¬ cording to the evaluation performed on th 45th day. The increase of herbicidal activity had no injurious effect on maize. Accordingly, it can be established that the com¬ pounds according to the invention when employed alone in the given doses could not control the most resistant monocotyledonous weed, wild millet. Their combinations with chloroacetanilide herbicides (which are ineffective or have only a slight effect alone), however, are cap¬ able of an effective control of wild millet and show an increased duration of activity, i.e. a clear synergism. is observed. Example 5a) Examination of the extension of activity, the extent of the reduction of dose, the possibility of com¬ bination of antidotes in case of combinations of chloro¬ acetanilide herbicides with the compounds of formula (I) The test conditions were identical with those described in Example 5. The following treatments v.ere carried out: 1) control 2) alachlor ,(2-chloro-2' ,6'-diethyl-N-methoxymethyl-acet- anilide) 2.0 kg/ha 3) alachlor 1.0 kg/ha 4) acetochlor (2-chlorc-2 , -methyl-6'-ethyl-N-methoxy- ethyl-acetanilide) 2.0 kg/ha 5) acetochlor 1.0 kg/ha 6) butachlor (N-butoxymethyl-2-chlorc-2- 5 ~ diethyl-acet- •--Λ,^V OB-Gff- - anilide) 4.0 kg/ha 7) butachlor 2.0 kg/ha 8) diethatyl (N-chloroacetyl-N-(2,6-diethylphenyl)- -glycine 4-0 kg/ha 9) diethatyl 2.0 kg/ha 10) dimethachlor (2-chloro-N-(2,6-dimethylphenyl)-N-(2- -methoxyethyD-acetamide 2.0 kg/ha 11) dimethachlor 1.0 kg/ha 12) pretylachlor (2-chloro-2' ,6'-diethyl-N-(2-propoxy- ethyl)-acetanilide 3.0 kg/ha 13) pretylachlor 1.5 kg/ha 14) propachlor (2-chloro-N-isopropylacetanilide) 6.0 kg/ha 15) propachlor 3.0 kg/ha 16) methazachlor (2-chloro-N-(2,6-dime hylphenyl)-N-(lH- -pyrazol-l-ylmethyl)-acetamide 3.0 kg/ha 17) methazachlor 1.5 kg/ha 18) metholachlor (2-chloro-N-(2-ethyl-6-methylphenyl)-N- -(2-methoxy-l-methylethyl)-acetamide) 2.0 kg/ha 19) metholachlor 1.0 kg/ha 20) alachlor 1.0 kg/ha + the product according to Example 2 500 g/ha 21) acetochlor 1.0 kg/ha + the product according to Example 2 500 g/ha 22) butachlor 2.0 kg/ha -. the product according to Example 2 500 g/ha 23) diethatyl 2.0 kg/ha + the product according to Example 2 500 g/ha 24) dimethachlor 1.0 kg/ha + the product according to Example 2 500 g/ha 25) pretylachlor 1.5 kg/ha + the product according to Example 2 500 g/ha 26) propachlor 3.0 kg/ha + the product according to Example 2 500 g/ha 27) methazachlor 1.5 kg/ha + the product according to Example 2. 500 g/ha 28) metholachlor 1.0 kg/ha + the product according to Example 2 500 g/ha 29) The product according to Example 2 500 g/ha The doses are expressed in the amount of ac- tive ingredient. Effect of the active ingredients on the killing ratio of wild millet (Panicum spp) No. of Killing in % of the control on the _.o.o_d_ϊ S to - * 5«- W ~ - . -** Example a) day 1 0 0 0 2 15 0 0 3 0 0 0 4 26 0 • " 0 5 0 0 0 6 0 0 0 7 0 0 0 8 0 0 0 9 0 0 0 10 37 0 0 11 6 0 0 12 16 0 0 13 0 0 0 14 0 0 0 15 0 0 0 16 0 0 0 17 0 0 0 18 17 0 0 19 0 0 0 20 100 84 52 21 100 100 81 22 100 17 40 No. of Killing in _> of the contrcιl on the treatments according to 15th 30th 45th Example a day 23 100 63 39 24 100 100 86 25 100 36 77 26 100 100 88 27 100 92 71 23 100 88 73 29 0 0 0 The results set forth in the Table show that the test herbicides were practically ineffective against wild millet (Panicum ssp.) when employed in the test doses alone. By combining the test herbicides with the compound according to Example 2 of the instant invention their efficiency could considerably be improved. Accord¬ ing to the evaluations carried out on the 15th day the herbicidal effect was 100 % in case of each combination, while even the results observed on the 45th day show that in spite of the lower doses employed, the activity was increased to an unexpected extent, which could not be foreseen on the basis of the individual activities of the components combined. Example 5b) The biological activity of acetochlor was exam¬ ined alone and in combination with the product according to Example 3 in maize. The test conditions were identical with those described in Example 5. The following treat¬ ments were carried out: 1) control 2) acetochlor 2.0 kg/ha 3) compound according to Example 3 400 g/ha - 13 - 4) acetochlor 2.0 kg/ha +- compound according to Example 3 400 g/ha 5) acetochlor 2.0 kg/ha -t- compound according to Example 3 400 g/ha + N-dichloroacetyl-l-oxy-4-aza-spiro-4,5- -decane 200 g/ha 6) acetochlor 2.0 kg/ha + N-dichloroacetyl-l-oxy-4-aza- spirodecane 200 g/ha The doses are expressed in the amount of active ingredient. During evaluation the height of maize was meas¬ ured to determine whether the compound according to Example 3 reduced the toxic effect of acetochlor on maize or had any effect on the similar effect of antidote (N- -dichloroacetyl-l-oxa-4-aza-spirodecane). Effect of the active ingredients on the height of maize in %. ol the control No. of Alteration in height in maize culture treatments on the according to 15th 30th 45th Example 5b) day 1 100 100 100 2 56 87 100 3 124 115 103 4 109 103 101 5 116 109 105 6 92 101 100 The results show that the compounds according to the invention counterbalance the toxicity of aceto¬ chlor and increase the efficiency of the antidote tested, Example 5c) 2'-Methyl-6'-ethyl-N-ethoxymethyl-chloroacet- anilide (acetochlor), 2-chloro-N-isopropylacetanilide (propachlor) and 2-chloro-2' ,6-*-diethyl-N-(methoxymethyl)- -acetanilide as typical representatives of chloroacet¬ anilide herbicides were combined with the compound accord¬ ing to Example 3 and a herbicidally active urea deriva¬ tive, chlorobromuron (3-(4-bromo-3-chlorophenyl)-l-aeth- oxy-l-methyl-urea). The test conditions were identical with those described in Example 5, except that in addition to mono- cotyledonous weeds also dicotyledons (Amaranthus retro- flexus) were sown. The following treatments were carried out: 1) control 2) 2'-methyl-6'-ethyl-N-ethoxymethyl-chloroacetanilide 2 kg/ha 3) 2-chloro-N-isopropylacetanilide 4 kg/ha 4) 2-chloro-2' ,6'-diethyl-N-(methoxymethyl)-acetanilide 2,5 kg/ha ) 3-(4-bromo-3-chlorophenyl)-l-methoxy-l-methyl-urea 1.5 kg/ha 6) compound according to Example 3 1.0 kg/ha 7) '-methyl-6'-ethyl-N-ethoxymethyl-chloroacetanilide 2.0 kg/ha + 3-(3-bromo-3-chlorophenyl)-l-methoxy-l- methyl-urea 1.5 kg/ha +• compound according to Example 3 1.0 kg/ha 8) 2-chloro-N-isopropylacetanilide 4 kg/ha + 3-(4-bromo- -3-chlorophenyl)-l-methoxy-l-methyl-urea 1.5 kg/ha + compound according to Example 3 1.0 kg/ha 9) 2-chloro-2' ,6'-diethyl-N-(methoxymethyl)acetanilide 2.5 kg/ha + compound according to Example 3 1-0 kg/ha 10) compound according to Example 3 0.4 kg/ha 11) 2'-methyl-6'-ethyl-N-eτhoxymethyl-chloroace anilide 2.0 kg/ha t- 3-(4-bromo-3-chlorophenyl)-l-methoxy-l- methyl-urea 1.5 kg/ha + compound according to Example 3 0.4 kg/ha 12) 2-chloro-N-isopropylacetanilide 4.0 kg/ha -. 3-(4- -bromo-3-chlorophenyl)-l-methoxy-l-me_hyl-urea 1.5 kg/ha + compound according to Example 3 0.4 kg/ha 13) 2-chloro-2' ,6'-diethyl-N-(methoxyme hyl)-acetanilide 2.5 kg/ha +- compound according to Example 3 0.4 kg/ha The effect of the active ingredients on the killing rate of wild millet (Panicum ssp) and amaranth (Amaranthus ssp). No. of Killingin _. of the control on ■ the treatments 15th 30th 45th according to day Example 5 c) ■ W.M. A.R. ..4. A.R. 7..M. A.R. 1 0 0 0 0 0 0 2 26 67 0 37 0 0 3 0 51 0 19 0 0 4 15 60 0 23 0 0 5 0 32 0 19 0 0 6 11 0 0 0 0 0 7 100 100 ICO 31 62 58 8 76 100 57 33 41 54 9 33 100 61 78 50 51 10 0 0 r - 0 0 0 11 92 100 75 78 54 53 12 59 100 43 31 29 60 13 77 100 56 74 37 62 W.M. = wild millet A.R. = amaranth Prom the results it can be concluded that the compounds according to the invention improve the duration and extent of activity of chloroacetanilide herbicides βw. σw β --'*- also in combination with herbicidally active urea deriva¬ tives. Example 5d) Under similar conditions to those described in Example 5 we examined the herbicidal activity of combina¬ tions of herbicidally active chloroacetanilides and tri- azines in association with the compound according to Example 1. As weeds wild millet (Panicum ssp) and amaranth (A aranthus ssp) were employed. The following treatments were carried out: 1) control 2) 2'-methyl-6'-ethyl-N-ethoxymethyl-chloroacetanilide 2.0 kg/ha 3) 2-chloro-4-ethylamino-6-isopropylamino-l,3,4-triazine 1.0 kg/ha 4) 2-ethylamino-4-isopropylamino-6-me hylthio-l,3,5-tri- azine 1.0 kg/ha 5) 2,4-bis(isopropylamino)-6-methoxy-l,3,5-triazine 1.0 kg/ha 6) 2-(4-chloro-6-ethylamino-l,3,5-triazine-2-yl-amino)- 2-methyl-propionitrile 1.0 kg/ha 7) compound according to Example 1 1.0 kg/ha 8) compound according to Example 1 0.4 kg/ha 9) 2'-methyl-6'-ethyl-N-ethoxymethyl-chloroacetanilide 2.0 kg/ha + 2-chloro-4-ethylamino-6-isopropylamino- -1,3,5-triazine 1.0 kg/ha *+• compound according to Example 1 1.0 kg/ha 10) 2'-methyl-6'-ethyl-N-ethoxymethyl-chloroacetanilide 2.0 kg/ha + 2-chloro-4-ethylamino-6-isopropylamino- -1,3,5-triazine 1.0 kg/ha + compound according to Example 1 0.4 kg/ha 11) 2'-methyl-6'-ethyl-N-ethoxymethyl-chloroacetanilide 2.0 kg/ha + 2-ethylamino-4-isopropyla ino-6-methyl- thio-l,3,5-triazine 1.0 kg/ha + compound according to Example 1 1.0 kg/ha 12) 2'-methyl-6'-ethyl-N-ethoxymethyl-chloroacetanilide 2.0 kg/ha -- 2-ethylamino-4-isopropylamino-6-nιethyl- -tnio-l,3,5-triazine 1.0 kg/ha +- compound according to Example 1 0.4 kg/ha 13) 2'-methyl-6'-e hyl-N-ethoxymethyl-chloroacetanilide 2.0 kg/ha + 2,4-bis(isopropylamino)-6-methoxy-l,3,5- triazine 1.0 kg/ha + compound according to Example 1 1.0 kg/ha 14) 2'-methyl-6'-ethyl-N-ethoxymethyl-chloroacetanilide 2.0 kg/ha + 2,4-bis(isopropylamino)-6-methoxy-l,3,5- -triazine 1.0 kg/ha + compound according to Example 1 0.4 kg/ha 15) 2'-methyl-6'-ethyl-N-ethoxymethyl-chloroacetanilide 2.0 kg/ha -. 2-(4-chloro-6-ethylamino-l,3,5-triazine- -2-ylamino)-2-methyl-propionitrile 1.0 kg/ha + com¬ pound according to Example 1 1.0 kg/ha 16) 2 3 -methyl- '-ethyl-N-ethoxymethyl-chloroacetanilide 2.0 kg/ha + 2-(4-chloro-6-ethylamino-l,3,5-triazine- -2-ylamino)-2-methyl-propionitrile 1.0 kg/ha + com¬ pound according to Example 1 0.4 kg/ha The effect of the active ingredients on killing rate .%) of wild millet (Panicum ssp) and amaranth (Amaranthus ssp) No. of Killing ratio (%) related to the control treatments on the according to 15th 30th 45th Example 5 d) day W.M. A.R. W.M. A.R. W._,l. A.R. 1 0 0 0 0 0 0 2 26 67 0 37 0 0 3 14 92 6 61 0 48 4 19 94 4 70 0 53 5 20 89 11 66 0 44 No. of Kill.ing ratio ( ) related to- the control treatments on the according to 15th 30th 45th Example 5 d) day W.M. A.R. W.M. A.R. W.M. A.R. 6 16 98 7 72 0 56 7 11 0 0 0 0 0 8 0 0 0 0 0 0 9 100 100 100 100 66 87 0 10 100 100 87 100 59 74 11 100 100 100 100 61 81 12 100 100 80 95 54 70 13 100 100 100 100 52 77 14 100 100 79 92 46 70 5 15 100 100 95 100 62 79 16 100 100 76 96 57 71 7..M. = wild millet A.R. = amaranth 0 As the results set forth in the Table above the compound according to Example 1 increased the activity and extended the duration of activity of combinations containing chloroacetanilides (2'-methyl-6'-ethyl-N- -ethoxymethyl-chloroacetanilide) and various triazines 5 in the usual doses and mutual proportions. Example 6 In this experiment the effect of the compound according to the invention on the duration of activity of ° thiolcarbamate herbicides and on their combinations with antidotes was tested. Tests were carried out as described in Example 5, except that, as usual in case of thiolcarbamate her¬ bicides, the compositions were admixed with the soil prior to sowing. The following treatments were carried out: 1) control 2) 3-e hyl-dipropylthiolcarbamate (ΞPTC) 5 kg/ha 3) S-ethyl-dipropylthiolcarbamate (EPTC) 5 kg/ha + N- -dichloroacetyl-l-oxa-4-azaspiro-4,5-decane 350 g/ha (AD-67) 4) S-ethyl-dipropyIthiocarbamate (EPTC) 5 kg/ha + 0,S-di- -2-chloroethyl-S-(di-2-propenylamino)-dithiophosphoric acid ester 500 g/ha (compound according to Example 2) 5) S-ethyl-dipropylthiocarbamate (EPTC) 5 kg/ha + N- -dichloroacetyl-l-oxa-4-azaspiro-4,5-dicane 350 g/ha (AD-67) + 0,S-di-2-chloroethyl-S-(di-2-propenylamino)- -dithiophosphoric acid ester 600 g/ha (compound accord- ing to Example 2) 6 ) N-dichloroacetyl-l-oxa-4-azaspiro-4, 5-decane 350 g/ha (AD-67) + 0 ,S-2-chloroethyl-S-(dI-2-propenylamino ) -di¬ thi phosphoric acid ester 500 g/ha (compound according to Example 2 ) 7) N-dichloroacetyl-l-oxa-4-azaspiro-4,5-decane 450 g/ha (AD-67) 8) 0,S-di-2-chloroethyl-S-(di-propenylamino)-dithiophos¬ phoric acid ester 500 g/ha (compound according to Example 2) The effect of active ingredients on the killing rate (%) of wild millet (Panicum SSP) No. of Killing rate in -age of the control treatments on the according to 15th 30th 45th Example 6 day 1 0 0 0 2 100 0 0 3 100 0 0 No. of Killing rate in ..-age of the control treatments on the according to 15th 30th 45th Example 6 day 4 100 100 90 5 100 97 80 6 0 0 0 7 0 0 0 8 0 0 0 The effect of active ingredients on the extent of injury of maize (Zea mays)-phytotoxicity No. of A Alltteration in height in ..-age of the treatments control according to 15t 30th 45th Example 6 day 1 100 100 100 2 69 100 100 3 82 100 100 4 94 100 100 5 121 110 106 6 134 118 111 7 102 100 100 8 129 120 108 The results show that under the provβcative conditions described in Example 5 the test compound of formula (I) extended the duration of activity of S-ethyl- -dipropyl-thiolcarbamate to three-fold of the activity observed when the herbicide was used either alone or in combination with the given antidote in the usual doses. It can be concluded, too, that the compound according to Example 2, selected as a representative of the compounds of formula (I), has no effect on the test weed when employed alone, in the given dose. It is highly surprising that the compound according to Example 2 sub¬ stantially extends the active period of thiolcarbamate herbicides even under provocative conditions (accelera¬ tion of decomposition) . Evaluation of the phytotoxicity studies shows that the test compound according to the invention reduces the undesired effect of thiolcarbamate " herbicides on the cultivated plant tested (maize). The same effect was ob¬ served when the combinations were antidoted. It can fur¬ ther be concluded that compounds of formula (I) are not phytotoxic themselves. The antidotal activity of the compounds ac- cording to the invention as well as their effect on the efficiency of a known antidote were tested by measuring the height of maize treated, and calculating the change related to the control. It can be seen that EPTC when used without any antidote decreased the height of maize by 31 % according to the evaluation performed on the 15th day. In case of antidoted EPTC combinations the reduction in height was 18 % only. In case of later sowings (evaluations carried out on the 30th and 45th days, respectively) there was no change in height. The combination of EPTC with the compound according to Example 2 resulted in a further reduction of the decrease in height: the decrease was only 6 % according to the evaluation performed on the 15th day. When the antidoted EPTC formulation and the active ingredient according to the invention were spray¬ ed together on maize (treatment No. 5), the height of the maize exceeded the height of the control. Combined application of the test antidote and the active ingredi- ent according to the invention resulted in a further in- crease in the growth of maize. Prom the results it can be concluded that the compounds according to the inven¬ tion increase the efficiency of antidotes of herbicidally active thiolcarbamates (N-dichloroacetyl-1-oxa-azaspiro- 4,5-decane; N,N-diallyl-2,2-dichloroacetamide; 3-(dichloro acetyl)-2,2-dimethyl-l,3-oxazolidine) . The results discussed in Example 6 unambi¬ guously prove that the active ingredients according to the invention on the one hand increase the activity of herbicidally active thiolcarbamates and extend the dura¬ tion of their activity, on the other hand, improve the selectivity of said herbicides and their combinations with antidotes and extend the period within which said formulations can be used safely. Example 6a) In this example the herbicidal activity, and the effective doses of herbicidally active thiolcarba¬ mates alone and in combination of compounds according to the invention were examined. The test conditions were identical with those described in Examples 5 and 6, except that the herbicidal activity and the duration of activity were examined. The following treatments were carried out: 1) control 2) butylate (S-ethyl-diisobutyl(thiolcarbamate )) 4.0 kg/ha 3) butylate 3 kg/ha 4) cycloate (S-ethyl-N-cyclohexyl-N-ethyl(thiolcarbamate )) 4 kg/ha 5) cycloate 2 kg/ha 6) vernolate (3-propyl-dipropyl(thiolcarbamate)) 4 kg/ha 7) vernolate 3 kg/ha 8) butylate 4 kg/ha + compound according to Example 3 1 kg/ha 9) butylate 3 kg/ha -. compound according to Example 3 0.75 kg/ha 10) cycloate 4 kg/ha + compound according to Example 3 1 kg/ha 11) cycloate 3 kg/ha + compound according to Example 3 0.75 kg/ha 12) vernolate 4 kg/ha + compound according to Example 3 1 kg/ha 13) vernolate 3 kg/ha -+■ compound according to Example 3 0.75 kg/ha 14) compound according to Example 3 1 kg/ha 15) compound according to Example 3 0.75 kg/ha The compositions were thoroughly admixed with the soil prior to sowing. The effect of the active ingredients on the killing ratio ( ) of wild millet (Panicum ssp) No. of Killing rate in -age of control treatments on the according ; to 15th 30th 45th Example 6•a) day 1 0 0 0 2 100 11 0 3 75 0 0 4 10 7 0 5 63 0 0 6 100 0 0 7 66 0 0 8 100 100 86 9 1Q0 77 52 10 100 100 81 11 100 80 60 12 100 100 . 54 13 100 33 59 No. of Killing rate in -age of control treatments on the according to 15th 30th 45th Example 6a) day 14 0 0 0 15 0 0 0 The test results show that the duration of the activity of herbicidally active thiolcarbamates can be expanded and their dose can be reduced, if they are com¬ bined with the active ingredients according to the in¬ vention. Example 6b) The increase in the duration of herbicidal ac¬ tivity and the decrease of their effective dose were tested in case of thiolcarbamate herbicides, which need not be admixed with the soil prior to sowing in order to achieve the desired effect. The test conditions were as described in Example 6. 1) control 2) diallate (S-2,3-dichloroallyl-diisopropyl(thiolcarba¬ mate) ) 1.2 kg/ha 3) diallate 0.6 kg/ha 4) triallate (S-2,3,3-trichloroallyl-diisopropyl(thiol¬ carbamate)) 2.0 kg/ha 5) triallate 1.0 kg/ha 6) pebulate (S-propyl-butyl(ethyl)thiolcarbamate) 3.0 kg/ha 7) pebulate 1.5 kg/ha 3) molynate ($-ethyl-N,N-hexamethylenethiolcarbamate) 3.0 kg/ha 9) molynate 1.5 kg/ha 10) sulfallate (2-chloroallyl-diethyl-dithiocarbamate) 4.0 kg/ha 11 sulfallate 2.0 kg/ha 12 diallate 1_2 kg/ha + compound No. 10.25 kg/ha 13 diallate 0.6 kg/ha + compound No. 10.125 kg/ha 14 triallate 2 kg/ha -+- compound No. 1 0.4 kg/ha 15 triallate 1 kg/ha + compound No. 1 0.2 kg/ha 16 pebulate 3 kg/ha + compound No. 1 0.5 kg/ha 17 pebulate 1.5 kg/ha + compound No. 1 0.25 kg/ha 18 molynate 3 kg/ha + compound No. 1 0.5 kg/ha 19 molynate 1.5 kg/ha -+- compound No. 10.25 kg/ha 20 sulfallate 4 kg/ha + compound No. 10.8 kg/ha 21 sulfallate 2 kg/ha -+- compound No. 10.4 kg/ha Unlike in the previous tests instead of wild millet (Panicum ssp) wild oat (Avena fatua) was used as a test plant, since the above-men ioned herbicides are particularly effective against wild oat, though they are active also against other monocotyledonous weeds. Th effect of the compounds according to the invention on the killing rate ( ) of wild oat (Avena fatua) No. of Killing rate in %-age of the control treatmen ;s on the accordingj to 15th 30th 45th Example ,)b) day 1 0 0 0 2 79 0 0 3 31 0 0 4 83 5 0 5 42 0 0 6 67 0 0 7 22 0 0 8 71 0 0 9 26 0 0 - l - No. of Killing rate in %-age of the control treatments on the according to 15th 30th 45th Example 6b) day 10 88 11 0 11 41 0 0 12 100 100 69 13 100 69 51 14 100 100 100 15 100 89 66 16 100 100 92 17 100 81 59 18 100 100 71 19 100 76 61 20 100 100 100 21 100 84 75 Examination of the thiolcarbamate herbicides shows that they are ineffective two weeks after the treatment. If, however, they are combined with compound No. 1 according to the invention, their activity lasts more than two-times as long as originally. In addition, their activity is also increased. Decreasing the dose of the thiolcarbamate herbicides tested but combining them with the compound No. 1, the death of wild oat is 100 % at the first evaluation even if the dose of the herbicide is decreased to half of its original amount. A more than 50 % death is observed even during the third evaluation (45th day) when a combination was employed, while the herbicides alone, even in the complete original doses, were ineffective (0 %) 45 days after treatment. Example 6c) The test conditions were the same as in Examples 5 and 6, except that in addition to wild millet (Panicum ssp) amaranth (A aranthus ssp) was used as a test weed. The following treatments were carried out: 1) control 2) S-ethyl-dipropylcarbamothioate 5.0 kg/ha + N-dichloro- acetyl-l-oxy-4-azaspiro-4,5-decane 0.5 kg/ha 3) s-ethyl-diisobutylthiocarbamate 5.0 kg/ha + N,N-di- allyl-2,2-dichloroacetamide 0.5 kg/ha 4) 2-chloro-4*-ethylamino-6-isopropylamino-l,3,5-triazine 1.5 kg/ha 5) 2-chloro-4-ethylamino-6-isopropylamino-l,3,5-triazine 0.75 kg/ha 6) 2-(4-chloro-6-ethylamino-l,3,5-triazine-2-ylamino)-2- methylpropyonitrile 1.5 kg/ha 7) 2-(4-chloro-6-ethylamino-l,3,5-triazine-2-ylamino)-2- methylpropionitrile 0.75 kg/ha 8) compound according to Example 3 1.0 kg/ha 9) S-ethyl-dipropylcarbamothioate 5.0 kg/ha + -dichloro- acetyl-l-oxa-4-azaspiro-4,5-dβcane 0.5 kg/ha + 2- -chloro-4-ethylamino-6-isopropylamino-l,3,5-triazine 1.5 kg/ha + compound according to Example 3 1.0 kg/ha 10) S-ethyl-dipropylcarbamothioate 5.0 kg/ha + N-dichloro- acetyl-l-oxa-4-azaspiro-4,5-decane 0.5 kg/ha + 2- chloro-4-e h la__.ino-β-isopropylamino-1 ,3, -triazine 0.75 kg/ha + -c αipound. according to. Example " 3 1.0 kg/ha.- - . . - . 11) S-ethyl-dipropylcarbamothioate 5.0 kg/ha + N-dichloro- acetyl-l-oxa-4-azaspiro-4,5-decane 0.5 kg/ha + 2-(4- -chloro-6-ethylamino-l,3,5-triazine-2-yl-amino)-2- -methyl-propionitrile 1.5 kg/ha + compound according to Example 3 1.0 kg/ha 12) S-ethyl-dipropylcarbamothioate 5.0 kg/ha + N-di- chloroacetyl-l-oxa-4-azaspiro-4,5-decane 0.5 kg/ha + 2-(4-chloro-6-ethylamino-l,3, -triazine-2-ylamino)- -2-methyl-propionitrile 0.75 kg/ha + compound accord- ing to Example 3 1.0 kg/ha 13) S-ethyl-diisobutyl-thiocarbamate 5.0 kg/ha + N,N-di- allyl-l,2-dichloroacetamide 0.5 kg/ha + 2-chloro-4- -ethylamino-6-isopropylamino-l,3,5-triazine 1.5 kg/ha + compound according to Example 3 1.0 kg/ha 14) S-ethyl-diisobutyl-thiolcarbamate 5.0 kg/ha + N,N- -diallyl-2,2-dichloroacetamide 0.5 kg/ha + 2-chloro- -4-ethylamino-6-isopropylamino-1,3,5-1riazine 0.75 kg/ha + compound according to Example 3 1.0 kg/ha 15) S-ethyl-diisobutyl-thiolcarbamate 5.0 kg/ha + N,N- -diallyl-2,2-dichloroacetamide 0.5 kg/ha + 2-(4- -chloro-6-ethylamino-l,3,5-triazine-2-yl-amino)-2- -methylpropionitrile 1.5 kg/ha + compound according to Example 3 1.0 kg/ha 16) S-ethyl-diisobutyl-thiolcarbamate 5.0 kg/ha + N,N- diallyl-2,2-dichloroacetamide 0.5 kg/ha + 2-(4- -chloro-6-ethylamino-1,3,5-triazine-2-yl-amino)-2- -methylpropionitrile 0.75 kg/ha + compound according to Example 3 1.0 kg/ha No. of Killing rate in %-aβe of the control on treatments the according to 15th 30th 45th Example oc) day W.M. A.R. W.M. A.R. W.M. A.R. 1 0 0 0 0 0 0 2 100 67 0 0 0 0 3 100 59 0 0 0 0 4 34 93 11 60 0 31 5 11 49 0 21 0 0 6 38 90 13 64 * 0 25 No. of Killing rate i .-age.of the control on treatments the according to 15th 30th 45th Example 6c) day_ W.M. A.R. W.M. A.R. W.M. A.R. 7 14 42 0 25 0 0 8 0 0 0 0 0 0 9 100 100 100 100 69 78 10 100 100 100 100 57 71 11 100 100 100 100 72 76 12 100 100 100 100 51 69 13 100 100 100 100 71 74 14 100 100 100 100 56 67 15 100 100 100 100 67 70 16 100 100 100 100 41 56 W.M. = wild millet A.R. = amaranth Thiolcarbamate herbicides are often combined with herbicidally active triazine derivatives, to widen their activity spectrum. Examination of the activity of the combina¬ tions containing herbicidally active thiolcarbamates, triazines and compounds according to the invention shows that the compound according to the invention extend the duration of activity and increase the activity of the test combinations. Accordingly, compounds of the formula (I) excert their favourable effects not only in combina- tion with thiolcarbamate herbicides alone but also if they are combined with various herbicidally active triazine derivatives. Example 7 The effect of the compounds according to the invention on the duration and extent of herbicidal ac¬ tivity of various herbicidally active thiolcarbamates were examined. The test were carried out essentially as 5 described in-Example 6, except that as a cultivated plant 5 pieces of soya were cultivated in each pot. The following treatments were performed: 1) control 2) l-methylethyl-3-chlorophenyl-carbamate 2 kg/ha ° 3) l-methylethyl-3-chlorophenyl-carbamate 1 kg/ha 4) l-methylethyl-3-chlorophenyl-carbamate 2 kg/ha + compound according to Example 3 0.5 kg/ha 5) l-methylethyl-3-chlorophenyl-carbamate 1 kg/ha -t- compound according to Example 3 0.5 kg/ha 5 6) l-methylethyl-3-chlorophenyl-carbamate 2 kg/ha + compound according to Example 1 0.25 kg/ha 7) l-methylethyl-3-chlorophenyl-carbamate 1 kg/ha + compound according to Example 1 0.25 kg/ha The effect of active ingredients on the killing rate (%) of wild millet (Panicum ssp) No. of Killing rate in -age of the control on treatments the according to 15th 30th 45th Example 7 day 1 0 0 0 2 23 0 0 3 8 00 0 95 64 40 5 74 - 53 29 6 97 73 55 7 66 41 30 The results set forth in the above Table show that l-methylethyl-3-chlorophenyl-carbamate alone is practically ineffective against wild oat in the test doses. The addition of the compound according to Example 1 has considerably increased the herbicidal activity in each combination tested, and the combinations which con¬ tained the compounds according to the invention were con¬ siderably more effective even on the 45th day after treat¬ ment than those containing the above-mentioned carbamate derivative as a sole active ingredient on the 15th day. The effect of the above combinations on cul¬ tivated plants was tested on soya. Injury rating was carried out on the basis of EWRC scale. 1 means that there was no injury observed, 9 stands for total killing. Phytotoxicity on soya using the combinations according to . ' the invention ; No. of Phytotoxicity (E7/RC) on the treatments according to 15th 30th 45th Example 7 day 1 1 1 1 2 2 1 1 3 1 1 1 4 2 1 1 5 1 1 1 6 1 1 1 7 1 1 1 it can be seen that the combination of 1- -methylethyl-3-chlorophenyl-carbamate with the compound according to the Invention resulted in no increase in phytotoxicity. Example 8 The effect of the combinations of thiolcarba¬ mate and chloroacetanilides with compounds of formula (I) was examined. Though they are generally applied to the fields differently (thiolcarbamates are to be incorporated into the soil while acetochlor should be sprayed on the sur¬ face), a common feature of thiolcarbamates and acetochlor is that both should be antidoted to avoid the undesired injury of cultivated plants (e.g. maize). Tests were carried out in pot having a diameter of 12 cm filled with meadow chernosiom soil, in 6 repe¬ titions. The corns of maize (5 pieces into each pot) were placed in a depth of 8 cm measured from the top of the pots. Corns were then covered with a 5 to 6 cm thick soil layer admixed with the seeds of various weeds (cocksfoots weed, amaranth). Weeds were admixed with the soil in separate pots, each with 1 cm of soil. The combinations tested were then sprayed on the pots as a tank mixture, in a amount of 220 lit./ha. After spraying, the soil was covered with a 2 to 3 cm thick fresh soil layer, and the water capacity of the soil was adjusted to 65 to 70 % _ On the 20th day after treatment the degree of weed control and the injury of cultivated plants were examined. On the 20th day the test plants were eliminated, and new weed seeds were admixed with the upper 3 to 5 thick layer of soil. The degree of weed control was exam¬ ined and the efficiency of weed control was examined on the 40th day. The following treatments were carried out: 1) control 2) S-ethyldiisobutylthiolcarbamate 3 kg/ha + N,N-di- allyl-2,2-dichloroacetamide 500 g/ha + 2-chloro-2- -methyl-6-ethyl-N-methoxyethylacetanilide 1.0 kg/ha 3) S-ethyl-diisobutylthiolcarbamate 2 kg/ha + N,N-di- allyl-2,2-dichloroacetamide 500 g/ha + 2-chloro-2- -methyl-6-ethyl-N-methoxyacetanilide 2.0 kg/ha 4) S-ethyl-dipropylcarbamothioate 4 kg/ha + N-dichloro- acetyl-l-oxa-4-azaspiro-4,5-decane 800 g/ha + 2- -chloro-2-methyl-6-ethyl-N-methoxyacetanllide 1.5 kg/ha 5) S-ethyl-dipropylcarbamothioate 3.5 kg/ha +• N-dichloro- acetyl-l-oxa-4-azaspiro-4,5-decane 800 g/ha + 2-chloro- -2-methyl-6-ethyl-N-methoxyacetanilide 2.0 kg/ha 6) S-propyl-dipropylcarbamothioate 2.5 kg/ha + N-dichloro- acetyl-l-oxa-spiro-4,5-decane 520 g/ha + 2-chlo>rα-2- -methyl- -ethyl-N-methoxyacetanilide 1.00 kg/ha 7) S-propyl-dipropylcarbamothioate 1.5 kg/ha -. N-dichloro- acetyl-l-oxa-4-azaspiro-4,5-decane 520 g/ha + 2-chloro- -2-methyl-6-ethyl-N-methoxyacetanilide 2.0 kg/ha 8) treatment No. 2 + 0,S-di-2-chloroethyl-S-(di-2- -propenyla ino)-dithiophosphoric acid ester (compound according to Example 2) 0.8 kg/ha 9) treatment No. 3 + 0,S-di-2-chloroethyl-S-(di-2- -propenylamino)-dithiophosphoric acid ester (compound according to Example 2) 0.8 kg/ha 10) treatment No. 4 + 0,S-di-2-chloroethyl-S-(di-2- -propenylamino)-dithiophosphoric acid ester (compound according to Example 2) 1 kg/ha 11) treatment No. 5 + 0,3-di-2-chloroethyl-S-(di-2- -propenylamino)-dithiophosphoric acid ester (compound according to Example 2) 1 kg/ha 12) treatment No. 6 -. 0,S-di-2-chloroethyl-S-(di-2- -propenylamino)-dithiophosphoric acid ester (compound according to Example 2) 0.7 kg/ha 13) treatment No. 7 + 0,S-di-2-chloroethyl-S-(di-2- -propenylamino )-dithiophosphoric acid ester (compound according to Example 2) 0.7 kg/ha The effect of combinations on the killing rate of cocksfoot weed (Echinoohloa ssp) and amaranth (Amaranthus ssp ) No. of Killing in -age of the control on the treatments 20th 40th day Ec. Am. Ec. Am. 1 1 0 0 0 0 0 0 0 2 100 100 32 14 3 100 100 27 31 4 100 100 27 29 5 100 100 35 36 6 6 1 10000 1 10000 2 288 21 7 100 100 36 33 8 100 100 72 69 9 100 100 88 74 10 100 100 79 71 1 111 1 10000 1 10000 8 877 78 12 100 100 64 79 13 100 100 67 76 Ec = cocksfoot weed Am = amaranth The killing rate was examined on the basis of green weight. Killing rate (%) = green weight in -age of the control- Effect of the combinations on the height of maize and the ratio of malformation No. of Height of plant Ratio of treatments in ..-age of the malformation control on the basis of the average of 6x5 plants 1 100.0 2 94 - 5 3 86.6 4 90.5 5 93.8 6 8 866..33 2 7 89.7 1 8 95.7 9 93.6 10 94.5 11 96 .9 12 91.7 13 93.2 Evaluation of the activity of antidoted combi- nations of various thiolcarbamates (butylate, EPTC, vernolate) and acetochlor shows that they have no sub¬ stantial phytotoxic effect on maize, if they are incor¬ porated into the soil not too deeply. In addition, these combinations show an excellent herbicidal activity ac- cording to the evaluation carried out on the 20th day. The results of the second evaluation show, however, that their herbicidal activity considerably decreases as a function of time. On the 40th day they can control only 14 to 36 % of the weeds tested. On the other hand, when 0,S-di-2-chloroe hyl-3-(di-2-propenylamino)-dithiophos- phoric acid ester according to the invention was added to the test combinations, they killed 64 to 88 % of the weeds at the time of second evaluation, too. Moreover, the com¬ pound according to the invention did not increase the phytotoxicity of the test combinations.

Claims: Claims 1. Composition for the extension and increase of the activity of herbicidal compositions containing as herbicidally active ingredient at least one carbamate and/or thiolcarbamate and/or chloroacetanilide and/or di¬ chloroacetanilide derivative and optionally antidotes therefore, which comprises at least one thio- or dithio¬ phosphoric acid ester of the formula (I) wherein R stands for identical or different alkyl, alk¬ enyl, isoalkyl, isoalkenyl, haloalkyl, halo- alkenyl, isohaioalkyl or isohaloalkenyl groups, each containing up to 4 carbon atoms; R' represents identical or different alkyl, alk¬ enyl, isoalkyl, isoalkenyl, haloalkyl, halo¬ alkenyl, isohaioalkyl, isohaloalkenyl groups, each containing up to 4 carbon atoms; X is oxygen or sulfur, X-, is oxygen or sulfur, with the proviso that at least one of the X-, groups is other than oxygen. 2. A composition as claimed in claim 1, in which the mutual proportion of the herbicidally active ingre¬ dient and the compounds of formula (I) is between 30:1 and 1:1, preferably 6:1 and 5:1. 3. A composition as claimed in claim 1, in which the mutual proportion of the herbicidally active thiolcarbamate and/or chloroacetanilide herbicides, anti- dotes and the compounds of formula (I) is 1 : 0.03-0.25 : : 0.05 - 0.50, preferably 1 : 0.07-0.12 : 0.15-0.25. 4. A composition as claimed in claim 1, in which the mutual proportion of the herbicidally active chloro- acetanilide, s-triazine or urea derivatives and the com¬ pounds of formula (I) is 4-6 : 0.5-1.5 : 1. 5. A composition as claimed in claim 1, in which the mutual proportion of the herbicidally active thiolcarbamate and s-triazine derivatives and the com- pounds of formula (I) is 4-6 : 0.5-1.5 : 1. 6. A composition as claimed in claim 1, which comprises as herbicidally active ingredient a combination of a thiolcarbamate and chloroacetanilide compound, op¬ tionally in combination with an antidote. 7. A composition as claimed in claim 1, which comprises as a herbicidally active chloroacetanilide 2- -chloro-2' ,6'-diethyl-N-methoxymethylacetanilide, 2- -chloro-2'-methyl-6'-ethyl-N-methoxyethylacetanilide, N- -butoxymethyl-2-chloro-2' ,6'-die hylacetanilide, N-chloro- acetyl-N-(2,6-diethylphenyl)-glycine, 2-chloro-N-(2,6- -dimethylphenyl)-N-(2-methoxyethyl)-acetamide, 2-chloro- -2' ,6'-diethyl-N-(2-propoxyethyl)-acetanilide, 2-chloro- -N-isopropylacetanilide, 2-chloro-N-(2,6-dirr_ethylphenyl)- -N-(lH-pyrazol-l-ylmethyl)-acetamide or 2-chloro-N-(2- -ethyl-6-methylphenyl)-N-(2-methoxy-l-methylethyl)-acet- amide. 8. A composition as' claimed in claim 1, which comprises as a herbicidally active thiolcarbamate S-ethyl- -diisobutyl(thiolcarbamate), S-ethyl-N-cyclohexyl-N-ethyl- (thiolcarbamate), S-propyl-dipropyl(thiolcarbamate) , S- -2,3-dichloroallyl-diisopropyl(thiolcarbamate) , S-ethyl- N,N-hexamethylenethiolcarbamate, S-propyl-butyl(ethyl)- thiolcarbamate, S-2,3,3-trichloroallyl-diisopropyl- (thiolcarbamate) or 2-chloroallyl-diethyl-dithio(carbamate)

Inventors: CZIBOR JANOS, KARSAI ISTVAN, KARSAI JOZSEF, KIS GYOERGY, KRESZTA TRAJAN, PALIK JOZSEF, ROZSAVOELGYI MIHALY, SEBESTYEN ENDRE, VARGA IMRE, CZIBOR, JANOS, KARSAI, ISTVAN, KARSAI, JOZSEF, KIS, GYOERGY, KRESZTA, TRAJAN, PALIK, JOZSEF, ROZSAVOELGYI, MIHALY, SEBESTYEN, ENDRE, VARGA, IMRE
Applicants: NITROKEMIA IPARTELEPEK
Application year: 1985
Main classification: A01N57
IPC codes: A01N37, A01N43, A01N47, A01N57, C07F9