HU182729B - Liquid weed killer preparation containing two agents for weeds of two cotyledons - Google Patents

Abstract

Two-component herbicidal agents. The compositions according to the invention contain from 20 to 90% by weight of the compounds of the general formula (I) in which R & ind1! and R & ind2! C & ind1-6! -Alkyl or -cycloalkyl, or together denote a hexamethylene group and the general formula II, wherein R & ind3 !, R & ind4! and R & ind5! are the same or different and are hydrogen or chlorine, and 0 to 70 wt .-% of liquid Verduennungsmitteln and 5 to 10 wt .-% of surface-active agents.

Description

FIELD OF THE INVENTION The present invention relates to a synergistic herbicidal composition for use as a bi-active herbicide comprising a thiolcarbarate derivative of formula (I) and a hexamethyleneimine derivative of formula (11) as a biologically active substance.

In formula (I), R 1 and R p are the same or different and are C 1 -C 6 alkyl or together represent hexamethylene.

In formula (11), R 2, R 4 and R 6 are the same or different and are hydrogen or chlorine. The many known her- Among the biocides, thiolcarbamates of formula (1) or combinations thereof with other herbicides such as trlazines and pyridazone derivatives are known.

Thiol carbamate active compounds of formula (I) and preparations thereof are described, for example, in the a

913,327, 3,037,853, 3,175,897, 3, 185,720. 3,198,786 and a

U.S. Patent Nos. 582,314; Hungarian Patent Nos. 157,558; and 160,635.

The use of thiolcarbamates as herbicides alone is not widespread in practice since they mainly control monocot weeds and at the same time damage the crop plants to be protected. For example, when such agents are used at the desired concentrations to control various weeds, severe weeding and sloughing of the crop can occur. As a result of crop damage, yields are reduced.

The combination of thiolcarbamates with trlazines is also not widespread in practice because of the emergence of weed species resistant to triazine herbicides, and the slow, accumulation of triazines in the soil, and the limited use of thiolcarbamate. To overcome these difficulties, for example, U.S. Patent Nos. 3,131,509 and 3,564,768 disclosed that crop seeds of the crop were treated with certain antibodies prior to planting. These antibodies are not very effective, so they are not widespread.

Subsequently, antidotal agents have been used to counteract the deleterious effects of thiol carbamates, either alone or in combination with other active ingredients, and / or to increase the resistance of the plants. Thiol-carbamate-type herbicidal compositions containing such antidoting agents are described in Hungarian patents' 165 736, 168 977 and 170 214.

The disadvantage of the antidote monolayer thiolcarbamates is that they mainly control monocotyledonous weeds, and their dicotyledonous herbicidal activity is low and uncertain.

In practice, it is the most widespread antidote. In addition to N.N-diallyl dichloroacetamide, the phytotoxicity properties of various acetamide derivatives have been extensively studied.

. One communication / Slit. Diacl. / 1976/143, §7 investigated the ability of a group of nitrogen-containing heterocyclic compounds to reduce the deleterious effects of thiolcarbamates. using a combination of E- (dichloroacetyl) -hexamethylenimine and Triallate / f, N-diisopropyl-S-trichloroallylthiolcarbate * in a ratio of 16: 1 to 1: 4, has no detrimental effect. .

The effect of dichloroacetamide derivatives is also described in two other papers / J. Agrlc. Food. Chem., 1978, 26, 1, 137-40; (1979), 27, 3, 543-7-7, which, on the one hand, describe the preparation of acetamide derivatives and, on the other hand, attempt to find a correlation between the molecular structure of the anti-antagonizing acetamides and thiocarbamates.

These studies were almost exclusively focused on the harmful properties of acetamide derivatives and did not include their herbicidal activity.

Bexamethyleneimine derivatives of the formula FYL /, as herbicides, alone or in combination, are not known in the art.

During studies on the development of the invention it has been found that the active compounds of formula / 1 / and / 11 / general -; wherein RI and R £ is the same or different C1-6 alkyl or together bexametiléncsoport, R ,, R ₄ and R _g herbicidal composition containing the same or vigorous hydrogen and chlorine atom in a ratio of -1: 0.05 to 1: 0.64 at a dose of 3-15 kg / ha eradicates both monocotyledons / Avena fatua, Cynodon dactylon, Digitaria ssp., Echinochloa ^ ssp., Eleusine sáp., Eragrostis ssp., Lolium ssp. / multi-flora /, Poa ssp. / annua /, Setaria black, Sorghum halepenae7, both dicotyledonous / Amarantbus ssp., Cbenopodium album, Lamlum amplexicoule, Linum Uaitatissimum, Folygonum ssp, Flantago lanceolata, Portulaca oleracea, Spergula arvensls, Stellaria n. even without the addition of the antidotes used in practice, it does not damage the crop. In our experiments, it has surprisingly been found that the composition containing the active compounds of the general formulas (1) and (11) has a small effect on the dicotyledonous weeds, which are poorly controlled by thiolcarbarnates and similarly by the acetamides, and have a synergistic effect.

For the biological and pharmacological study of the herbicidal composition according to the invention, MVFV-26 and MVTC-596 hybrid maize (Zea maya / L / -7) was used as the test crop, since it is the most sensitive crop to thiolcarbamate type compounds. field of application.

The biological activity of the herbicidal composition containing the two active substances according to the invention was investigated in factual dishes and in a petri dish agar agar bioassay.

The pot test assay was performed as follows; Into plastic factories with a surface of 1.2 da 'we weighed 500500 g of soil sieved through a sieve with a diameter of 2 mm, followed by 4-4 grains of MVFV-26 hybrid maize / Zea maya 7L / -t7 and 0.30.3 g of Polygonum ssp, Setaria. ssp., and Plantagő lanceolate weed seeds were sown. A further 100 g of soil was added thereto, followed by treatment with the herbicide combination according to the invention as described in Example 19, and after treatment 200 g of soil was added to each culture vessel. The experiments were repeated three times * ·. · _O

During the experiments the average daily temperature was 24 * 3 C and the daily average relative humidity was 54.8%. The plants

It was reared under a 400 W sunlight lamp using an illumination period of -3182,729 hours. Water loss was replaced daily »Evaluation was performed on the 14th day after treatment.

The experimental results are shown in Table I.

Table I treatments length of shoot of corn corn green% cm% g%

untreated

control 40.2 100 6.8 100 4 .......... 38.1 94.7 6.8 100 34.5 85.8 5.9 86.8 SZD + 18.6 + 24.6 p = 5%

A ·, = 5.6 kg / ha N, N-di / n-propyl / -S-ethylthiolcarbamate +0.56 kg / ha N- (dichloroacetyl) -hexamethylenimine = 5.6 kg / ha ha N, N-di / n-propyl-S-ethylthiolcarbamate + 0.56 kg / ha N- (trichloroacetyl) -hexamethylenimine.

In the case of the combination “Αχ” the corn was intact, while in the case of the combination “Βχ” there was a slight deformation and twisting.

The agar-agar bioassay was performed as follows;

Agar agar (0.4% / medium) was added to the petri dish

300-300 ml and combinations of "A ₂ " or Bg "according to Example 19". Six to six seeds of MVFV-26 hybrid maize (Zea jnays // L) were seeded on the surface of the poured and solidified medium. The experiments were repeated three times · The evaluation was performed on the 7th day after the setup.

The experimental results are shown in Table II. Table.

II. spreadsheet

treatments shoot length zöldsuly cm % β % untreated control 10.7 ' 100 1 »? 100 42 10.9 101.9 1.75 102.9 6.9 64.5 1.55 91.2

-4182.729

Ρ - 5% + 50.4 + 40

Α ~ = 0.5θ kg / ha, N, N-di / n-propyl / -S-ethylthiolcarbamate + 0.056 kg / ha N- (dichloroacetyl) -hexamethylene imine.

Bp = 0.56 kg / ha for N, N-di / n-propyl / -S-ethylthiolcarbamate + 0.056 kg / ha for N- (trichloroacetyl) -hexamethylenimine.

Cassette test assays were performed on N, N-dl-n-propyl-S-ethylthiolcarbamate and N- (dichloroacetyl) -hexamethyl} -enimine and N, N-hexamethylene-S-ethyl-. for the biological effect of altering the ratio of thiolcarbamate to N- / dichloroacetyl / hexamethyleneimine, as follows:

the test plants were grown in plastic factories with a total of 700 g of meadow soil in soil with 12-hour illumination periods, under 400 W of sunlight, in plastic factories with a surface area of 1.2 da *. The total water capacity of the water replenishment was 65% lg daily. The weed seeds (Echinochloa crus galli, Setaria glauca, Chenopodium album and Linura usitatissimum) and the cultivated plant (MVTO-596 hybrid maize / 400 g air-dried, 2 mm sieve) were weighed.

It was covered with 200-200 g of soil and sprayed with the appropriate amount of herbicides of Examples 28 and 29 ·. After chemical treatment, a further 100 g of soil / pot was added. Evaluation was made on the 12th day after treatment, measuring the shoot length and green weight of maize and the green weight of monocotyledonous and dicotyledonous weeds. The results were analyzed by variancla analysis.

the herbicidal activity of N- / dichloroacetyl / hexamethyleneimine in itself and its effect on the green weight of maize

III. whereas the efficacy data for the combinations are given in Table IV. Table 9 shows the calculated data according to Colby S.R. with the formula / ^ alcuting Slnergistic and Antagonistic Responses of Herbicide Combinations, Weed, Vol.

15 · No. 1. 20-22. ρ. / 1967/7.

III. spreadsheet

The dose of N- (dichloroacetyl) -hexamethylen-lmin is kg / ha Green succulent corn % Monocotyledonous Dicotyledonous moc green weeds % its weight % untreated control 100 100 100 0.0049 . 96.5 44 51 0.049 78.5 52 43 0.098 95 ........ 47.5 49 0.196 89 66 43 0.392 88.5 57 52.5 .784 84 74 43 1,568 80.5 74 62 5.156 . 77 46.5 50 4,900 75.5 57 55

-5182.729

ARC. spreadsheet

A, active- Dicotyledon B active ¹ weed substance material kg / ha sludge kg / ha

Dicotyledon A, + B \ gZta Green Juice%

Green factories of dicotyledonous weeds were found in fact

10 16.2 0.4 52.5 10 + 0.4 5.2 8.5 10 16.2 0.8 43 10 + 0.8 0 6.97 10 16.2 1.6 62 10 + 1.6 0 10.04 10 16.2 3.2 30 10 + 3.2 0 4.86 10 16.2 4.0 52.5 10 + 4.0 0 7.14

A ₂ acts - A ₂ + B

Material ....................

5 23.03 0.4 52.5 5 ± 0.4 7.89 12.09 5 23.03 0.8 43 5 + 0.8 4.61 9.90 5 23.03 1.6 62 5 ± 1.6 5.92 14.28 10 29.61 0.25 43 10 + 0.25 6.58 12.73 10 29.61 0.50 52.5 10 + 0.50 0.00 15.54 10 29.61 0.8 43 10 + 0.8 5.26 12.73 10 29.61 1.6 62 10 + 1.6 3.29 18.36 10 .....- --- 29.61 ....... 3.2 ....... ..................... 30 10 + 3.2 5.26 8.88

Active ingredient A-j: N, N-diisobutyl-S-ethylthiolcarbamate

Active ingredient ₂ : N, N-di / n-propyl / -S- / n-propyl / thiolcarbamate

Active ingredient B: N- (dichloroacetyl) -hexamethylenimine

From the data in the tables it is clear that the herbicidal composition according to the present invention is effective in controlling the dicotyledonous weeds and does not damage the crop, so that the combination kills the dicotyledonous plants in excess of the additive effect of thiolcarbarate and dichloroacetamide.

Compounds of the formula Y1f used in the herbicidal composition wherein Rx, R4 and R5 are the same or different and are hydrogen or chlorine are prepared as described in the following examples, which are not included in the patent.

Example 1

4.9 µg (0.25 mol) of aoethyl chloride are mixed with 50 ml of acetone and then stirred. place in a flask fitted with a thermometer and a separatory funnel. The mixture was cooled with a salt-ice mixture.

The funnel was charged with a mixture of 50.58 g (0.51 mol) of hexamethylenimine and 50 ml of acetone, which was added to a mixture of acetylchloride and aoeton at 5-10 ^° C with stirring. Completion of S D Subsequent stirring at room temperature for one hour. Then, after approx. dry hydrogen chloride gas for twenty minutes

-6182.729 through the reaction mixture. If the reaction mixture is free from hexamethyleneimine, as determined by TLC, the hexamethyleneimine hydrochloride is removed from the reaction mixture by filtration and the filtrate is evaporated in vacuo to acetone.

The resulting H-acetylhexamethylenimine imine is a slightly yellow crystalline solid, m.p. 85-87 ° C. '

Yield: 33.48 g (95% of theory)

Analysis: Calculated: N, 9.92; found: 9.98%

Example 2

Chloroacetyl chloride (28.23 g, 0.25 mol) was dissolved in acetone (50 mL) at room temperature with stirring, then transferred to a flask equipped with stirrer, thermometer and addition funnel. The mixture was cooled with a salt-ice mixture. The addition funnel was charged with a mixture of 50.58 g (0.51 mol) of hexamethylene-lmin and 50 ml of acetone, which was added to a solution of chloroacetyl chloride in acetone at 5-10 ° C with stirring. After the addition is complete, 10-15C. at a temperature of one hour after mixing.

The reaction mixture was poured into nearly three times the volume of ice water with stirring, and the organic and aqueous layers were separated.

The organic phase is washed with an equal volume of 0.1 N hydrochloric acid and separated after settling.

The organic phase is washed again with water until the wash water is neutral and then dried over sodium sulfate. The acetone enters the aqueous phase.

The thus obtained N- (chloroacetyl) -hexamethylenimine imine is a slightly yellow liquid with a refractive index _n 20 _t 1.5064; _n 70. _{1> 4889}

Yield: 41.68 g 95% of theory ·

Analysis:

Calculated N: 797%; Found: C, 20.22; N, 7.92; Found: Cl, 20.46%.

Example 3 ______ Dichloroacetyl chloride (37 g, 0.25 mol) was dissolved in 50 ml of acetone at room temperature with stirring, then filled into a flask equipped with stirrer, thermometer and addition funnel.

The mixture was cooled with a salt-ice mixture. The addition funnel was loaded · Juk 5θ, 58 g / 0.51 mole / of hexamethyleneimine in 50 ml of acetone is treated by methylene chloride in acetone was added with stirring at 5 ^Ί0 θ 0th After the addition is complete, the mixture is stirred for one hour at 10-15 ° C.

The reaction mixture was poured into nearly three times the volume of ice water with stirring, and the precipitated solid was filtered off with suction and suspended in 0.1 N hydrochloric acid. After sedimentation, the hydrochloric acid phase is filtered off with suction and washed with water until the wash water is neutral and then dried.

The thus obtained N- (dichloroacetyl) -hexamethylenimine imine is a slightly yellowish, slightly yellow, porous material, m.p. 52-54 ° C, refractive index η'θ: 1.504-0.

Yield: 48.3 g, 92% of theory.

-7182.729

Analysis:

Calculated N: 6.66%; Cl, 33.80; Found N, 6.51; found Cl; 33.85%.

Example 4.

Trichloroacetylchloride (45.5 g, 0.25 mol) was dissolved in acetone (50 mL) at room temperature with stirring, and filled into a flask equipped with a stirrer, a beaker and a separatory funnel. The mixture was cooled with a salt-ice mixture. The addition funnel is charged with a mixture of 5Ο, 5θ g of _o / 0.51 mol / hexamethyleneimine in 50 ml of acetone, which is added to a solution of trichloroacetyl chloride in acetone at 5-10 ° C with stirring.

After the addition is complete, the mixture is stirred for one hour at 15-20 ° C. The reaction mixture was poured into nearly three times the volume of ice water with stirring, and the organic and aqueous layers were separated. The organic phase is washed with an equal volume of 0.1 N hydrochloric acid and separated after settling.

The organic phase is washed again with water until the wash water is neutral, then dried over sodium sulfate and filtered.

The acetone enters the aqueous phase.

The thus obtained N- (trichloroacetyl) -hexamethylene-lmin brown-red liquid has a refractive index of "20 in%: 1.5253? : 1.5060.

Yield: 57.45 g, 94% of theory. - °

Analysis: Calculated: N, 5.72; Cl, 43.55;

Found: N, 5.36; Found: Cl, 42.97%.

An herbicidal composition according to the present invention comprising 20 to 90% by weight of a compound of formula (I) and (11), wherein Bf. and B ₂ may be the same or different C 1 -C 6 alkyl, or together may be hexamethyl, while R x, B ₄ and B ₅ may be the same or different and represent hydrogen or chloro atom, preferably in the form of a liquid erosion concentrate. Compounds of formula I are in liquid form.

In the forming process, 19.8-89 parts by weight of a compound of formula (I) are weighed in an amount of 0-70 parts by weight of a liquid diluent, preferably kerosene, or aliphatic or aromatic chlorinated hydrocarbons, or aromatic hydrocarbons, or dimethylformamide, then 0.2-45 parts by weight of compound (YL) are added under stirring.

After stirring until complete dissolution, 5 to 10 parts by weight of surfactant, preferably anionic and nonionic, are added _; a mixture of surfactants such as a mixture of the calcium salt of dodecylbenzenesulfonic acid and a polyoxyalkylphenols or a mixture of the calcium salt of an alkylaryl azulfonic acid and an alkylphenylpolyglycol ether.

After homogenization, filter if it contains floating impurities.

The formulation is illustrated by the following examples, which are not to be construed as limiting the scope of the patent.

Example 5

With a stirrer, a thermoformed beaker is weighed with 10 µg of 98% active ingredient in N, N-di / n-propyl / -S-ethylthiolcarb

-8182.729 matt and 68 g of kerosene were added followed by stirring with 10 g of N- (dichloroacetyl) -hexamethyleneimine. Stir for 30 minutes at room temperature. then 8 g of Atlox 3400 B and 12 g of Atlox 4857 B emulsifier are added.

Stir for another 30 minutes and filter. 200 g of an emulsion concentrate are obtained with a total active ingredient of 110 g. A mixture of the calcium salt of Atlox 3400 B and Atlox 4857 B dodecylbenzenesulfonic acid and polyoxyethylene / alkyl phenols are manufactured by Atlas Chemie GmbH.

Example 6

163 g of 98% N, N-di / n-propyl / S-ethylthiolcarbamate and 20 g of N- (dichloroacetyl) -hexamethylenimine are added to a thermoformed round-bottom flask with stirring, followed by 35-40 ° C. and stirred for 30 minutes. Then 20 g of emulsifier 1-40 emulsifier are added and stirred for another 30 minutes and then filtered.

An emulsion concentrate of £ 00 g is obtained which has a total active ingredient content of 180

Emulsogen 1-40 emulsifier is a mixture of alkyl arylsulfonic acid calcium oxide and alkylphenyl poly / glycol ether / manufactured by Hoechst.

Example 7

146 g of 98% N, N-di / n-propyl / -S-ethylthiolecarbamate and 20 g of kerosene are added to a thermoformed round-bottomed flask, and 16 g of N / dichloroacetyl / hexamethyleneimine are added with stirring. and stirred at 35-40 ° C for 30 minutes. Then, 8 g of Atlox 3400-B and 12 g of Atlox 4857 B emulsifier were added and stirred at 35-40 ° C for 30 minutes and then filtered.

200 g of emulsion concentrate with a total active substance content of 159 g ·

Example 8

In the same manner as in Example 7, except that 20 g of dichloroethane is used as a solvent instead of 20 g of kerosene.

In the same manner as in Example 7, except that 20 g of dimethylformamide is used as the solvent instead of 20 g of kerosene.

Example 10

In the same manner as in Example 7, except that 20 g xylene is used as solvent instead of 20 g kerosene.

Example 11

Example 7 is followed in the same manner except that 20 g of chlorobenzene is used as the solvent for Jogy, instead of 20 g of kerosene.

Example 12

In the same way as in Example 7, except that

-9182.729 to replace 20C dimethylsulfoxide instead of 2C g of kerosene.

Example 13

N, N-di-n-propyl / -S-eth31-thiolcarbamate (73 g, 98%) and 14 g of kerosene were added under stirring to a thermoformed flask, and 8 g of K- / dichloroacetyl / hexamethylene were added thereto with stirring. and stirred at 35-40 ° C for 30 minutes. Thereafter, 6 g of Emulsogen 1-40 emulsifying agent were added and the mixture was stirred at 35-40 ° C for 25 minutes and filtered through a plug. 100 g of an emulsion concentrate with an active ingredient content of 80 g are obtained

Example 14

146 g of 98% N, N-di / n-propyl / -S-ethylthiolcarbamate and 28 g of kerosene are added to a thermometer-filled round-bottom flask and 14.6 g of N- (trichloroacetyl) - are added with stirring. hexamethyleneimine and stirred at 30-35 ° C for 15 minutes. 12 g of Emulsogenic 1-40 'emulsifier are then added and the mixture is stirred at 35-40 ° C for 25 minutes and then filtered.

200 g of an emulsion concentrate are obtained having a 158 g total volatility.

Example 15

146 g of 98% N, N-di / n-propyl / -S-ethylthiolcarbamate and 20 g of xylene were added to a round-bottomed flask equipped with a thermometer and stirred. 14.6 g of N- (chloroacetyl) -hexamethylen-amine are added with stirring and the mixture is stirred at 35-40 ° C for 30 minutes. Then, 8 g of Atlox 3400 B and 12 ”g of Atlox 4857 B emulsifier were added and stirred at 55-40 ° C for 30 minutes and then filtered.

200 g of an emulsion concentrate having a total active substance content of 158 g are obtained.

Example 16

146 g of 98% N, N-di / n-propyl / -S-ethylthiolcarbamate and 20 g of xylene are added to a thermoformed round-bottomed flask, and 14.6 g of N-acetylhexamethyleneimine are added with stirring. Stir at 35-40 ° C. Then 8 g of Atlox 3400 B and 12 g of Atlox 4857 B emulsifier were added and stirred at 35-40 ° C for 30 minutes and then filtered.

200 g of an emulsion concentrate having a total active substance content of 158 g are obtained,

EXAMPLE 17 150 g of N, N-hexamethylene-S-ethylthiolcarbamate and 18.5 g of kerosene were weighed into a round-bottomed flask with a thermometer and 12 g of N- (dichloroacetyl) -hexamethyleneimine and 25-30 g of Stir at 15 ° C for 15 minutes. Then, 4 g of Atlox 3400 B and 16 g of Atlox 4857 B emulsifier were added and stirred at 25-30 ° C for 15 minutes and then filtered.

200 g of an emulsion concentrate having a total active ingredient of 162 g are obtained.

-10182,729

Example 18 150 g of omb, Ν-hexamethylene-S-ethylthiolcarbamate and 28.5 g of xylene are charged into a round-bottomed flask equipped with a crusher and a thermometer, and 92 92 g of N- (dichloroacetyl) -hexamethylene imine and 35-are added. Stir at 40 ° C for 30 minutes. Thereafter, 6 g of Atlox 3400 B and 24 g of Atlox 4857 B emulsifier aza and 35-40 are added.

Stir at C for 15 minutes and filter.

300 g of an emulsion concentrate having a total active ingredient content of 242 g are obtained.

Example 19 Into a round-bottomed flask equipped with a crusher, a thermometer, 36.7 g of N, N-di / n-propyl / -S-ethylthiolcarbamate and 140 g of kerosene were weighed and 4 g of N- (dichloroacetyl) -hexamethylene and stirred at 20-25 ° C until dissolved. Then, 8 g of Atlox 3400 B and 12 g of Atlox 4857 B emulsifier were added and stirred at 20-25 ° C for 25 minutes and then filtered.

200 g of emulsion concentrate with an active ingredient content of 40.7 6 · are obtained.

Example 20

176 g of N, N-hexamethylene-S-ethylthiolcarbamate and 6 g of kerosene were charged into a round-bottomed flask equipped with a thermometer; then 4 g of N- (dichloroacetyl) -hexamethyleneimine are added with stirring.

After stirring at room temperature for 14 minutes, 14 g of Atlox 4857 B emulsifying agent are added.

After stirring for another 30 minutes, it is filtered to give 200 g of an emulsion concentrate with a total active ingredient of 180 g.

Example 21

80 g of N, N-hexamethylene-S-ethylthiolcarbamate and 24 g of dimethylformamide are added to a thermoformed round-bottomed flask and 80 g of N- (dichloroacetyl) -hexatoethyleneimine are added with stirring and the mixture is stirred for 15 minutes at room temperature. Then, 2 g of Atlox 3400 B and 14 g of Atlox 4857 B emulsifier are added and filtered after stirring for 3θ minutes.

200 g of an emulsion concentrate having a total active substance content of 160 g are obtained.

EXAMPLE 22 176 g of N, N-diisobutyl-S-ethylthiolcarbamate and 4 g of dimethylsulfoxide were charged into a round bottom flask with a thermometer and 4 g of N- (dichloroacetyl) -hexapethyleneimine were added with stirring. Stir at room temperature for 30 minutes. After adding 3 g of Atlox 4857 B _o and 13 g of Atlox 3400 B emulgeálóazert. The mixture is stirred at 35-40 ° C for 30 minutes and then filtered.

200 g of an emulsion concentrate having a total active substance content of 180 g are obtained.

Example 23

With stirring, 145 g of H, N-diisobutyl-S-ethylthiolcarbamate and 20 g of xylene are charged into a round-bottomed flask equipped with a thermometer; while stirring, 15 g of N- (dichloro-aoethyl) -hexamethyleneimine are added. The mixture was stirred at room temperature for half an hour and then added

4 g of Atlox 4857 B and 16 g of Atlox 3400 B emulsifier are added.

Stir another 30 minutes and filter.

200 g of emulsion concentrate are obtained with a total active ingredient of 160 g.

Example 24

70 g of N, N-diisobutyl-S-ethylthiolcarbamate and 20 g of chlorobenzene are charged into a round-bottomed flask equipped with a thermometer and 70 g of N- (dichloroacetyl) -hexamethylene-1 ml are added with stirring. After stirring for 30 minutes at room temperature, 4 g of Atlox 3400 B and 16 g of Atlox 4857 B emulsifier are added. Stir again for 30 minutes and filter.

200 g of an emulsion concentrate with a total active substance content of 140 g are obtained.

25 · example

Stirrer, thermometer, was charged with 176 g of N, N-di / n-propyl / S / n-propyl / -tiolkarbamátot _r and 8 g of kerosene was added 4 g N / diklór4acetil / hexamethylene imine stirring. After stirring at 35-40 ° C for 15 minutes, 12 g of Tensiofix 7438 emulsifier are added.

Stir for half an hour and then filter.

200 g of an emulsion concentrate are obtained with a total active ingredient of 180 g.

A mixture of Tensiofix 7438 alkyl phenol oxyethylene oxypropylene condensate and alkyl aryl sulfonic acid calcium is manufactured by Tensia S.A.

Example 26

145 g of N, N-di / n-propyl / S- / n-propyl / thiolcarbamate and 24 g of kerosene are added to a thermoformed round-bottomed flask and 15 g of N- / dichloroacetyl / hexamethyleneimine are added with stirring. . After stirring at room temperature for 30 minutes, 16 g of Tensiofix 7438 emulsifier are added.

After stirring for another 30 minutes, filter.

200 g of emulsion concentrate are obtained with a total active ingredient of 160 g.

27 · example

With stirring, a thermometer was charged with 70 6 N, N-di / n-propyl / S- / n-propyl / thiolcarbamate, 20 g xylene and 20 g dimethylformamide. 70 g of N- (dichloroacetyl) -hexamethyleneimine are added with stirring. Stirring was continued for 30 minutes at room temperature; and then 20 g of Tensiofix 7438 emulsifier are added.

Stir for another 30 minutes and then soak.

200 g of an emulsion concentrate are obtained with a total active ingredient content of 140 g.

Example 28

With stirring, 36.7 g of Ν, Ν-diisobutyl-S-ethylthiolcarbamate and 140 g of kerosene are weighed into a round-bottom flask equipped with a thermometer and 4 g of N- / dichloroacetyl / hexamethylene imyl and 20-25 ° C are added with stirring. stir until dissolved. Then, 8 g of Atlox 3400 B and 12 g of Atlox 4857 B emulsifier were added and stirred at 20-25 ° C for 25 minutes and then filtered.

-12182,729

200 g of an emulsion concentrate with 40.7 g of active ingredient are obtained.

29 · example

The procedure described in Example 28 was followed, except that 36.7 g of N, N-di / n-propyl / -S- / n was replaced with 36.7 g of 36, Ν-diisobutyl-S-ethylthiolcarbamate. -propyl / -thiolcarbamate is weighed.

Claims (2)

....... Patent Claims A liquid herbicidal composition for dicotyledonous weeds comprising two biologically active substances and liquid carriers, preferably kerosene * or aliphatic or aromatic chlorinated hydrocarbons or aromatic hydrocarbons or dimethylsulfoxide or non-methyl-formamide and surfactants. ionic surfactant mixture, characterized in that it contains a thiolcarbamate derivative of the general formula (1) and the compound of the general formula (11) in an amount of from 20 to 90% by weight and a ratio of 1: 0.05 / - / 1: 0.64 / a hexamethyleneimine derivative represented by the general formula (1): _{Χ χ} ^B 2 has the ^{same or} different substituent and C 1 -C 6 alkyl group or together the hexamethylene group; in formula (11) This, E / j. and Br is the same or different and represents a hydrogen or chlorine atom. An embodiment of the formulation according to claim 1, characterized in that it is present in an amount of 20-90% by weight and / l: 0; 05/1: 0.64 / wt / l / general cuplethyl thiol arm of a brown derivative; a hexamethyleneimine derivative of general formula (I), wherein Ep, Bp, Ez, E4 and Et in formulas (1) and (11) are as defined above and in an amount of 0-70% by weight of a liquid carrier, preferably kerosene or aliphatic or an aromatic chlorinated hydrocarbon, or an aromatic hydrocarbon, or dimethylsulfoxide, or dimethylformamide, and 5-10% by weight of a surfactant, preferably a mixture of anionic and non-ioponic surfactants.