DE3818147A1 - SULFONYLCARBAMIDE DERIVATIVES AS AN ACTIVE SUBSTANCE AND HERBICIDE COMPOSITION CONTAINING AN ANTIDOTUM GLYCINAMIDE DERIVATIVES - Google Patents

Abstract

The invention relates to herbicide compositions containing a sulfonylurea derivative of formula (I> <IMAGE> as herbicidally active ingredient and an N-dichloroacetyl-N-substituted-N', N'-disubstituted glycinamide derivative of formula (II> <IMAGE> as antidote, together with carriers as well as diluents and additives commonly used in the formulation of plant-protecting compositions.

Description

The invention relates to an active ingredient a sulfonylcarbamide derivative of the general formula (I)

and as an antidote an N- (dichloroacetyl) -N-substituted- glycine-N ′, N′-disubstituted-amide derivative of the general my formula (II)

containing herbicidal composition, which in maize and Crop millet works very selectively.

The sulfonyl carbamide derivatives, especially the Group of benzenesulfonyl carbamides, won since 1955 as an oral anti-diabetic, later as an anti-epileptic kum great importance.

20 years later, a herbicide was also discovered or regulating plant growth Effect of these compounds, and since then the Sulfonylcarbamide derivatives the most outstanding results nisse in herbicide research. There were many things Derivatives made and described, for example the 1,2,4-triazinyl derivatives (U.S. Patent No. 4,120,691) which 1,3,5-tiazinyl derivatives (U.S. Patent No. 41 27 405, 41 69 719, Hungarian Offenlegungsschriften No. T / 31 954, T / 35 475 and T / 39 322), pyridyl derivatives (DE 32 34 451), pyrimidyl derivatives (U.S. Patent No. 4,339,266, Hungarian Patent publications No. 1 80 731 and 1 89 212, Hungarian Open T-36 674), pyrazole derivatives (Hungarian T-35 480), indole derivatives (Hungarian Application No. T / 30 918), thiophene derivatives (Hungarian Patent No. 1 90 675, Hungarian German Offenlegungsschrift No. T / 28 604, T / 30 169, T / 30 489).

Much of the previously known specialist literature describes the herbicidal and the plant growth regulating effect of 1,3,5-triazinyl or pyrimi dinyl derivatives alone (Hungarian patents No. 1 81 423, 1 81 869, 1 88 629, 1 90 702, 1 91 006, EP-PS 00 71 958, Hungarian publications No.T / 30 871, T / 34 167, T / 37 859, T / 37 868) or in Combination with other active ingredients, for example with  Iso (thio) carbamide derivatives (US Pat. No. 43 39 267), with triazinedione derivatives (Hungarian disclosure Font No. T / 31 952) or with the most varied Carbamide, carbamate, uracyl, triazine, phenoxy or propionic acid derivatives (Hungarian disclosure publications No.T / 39 338, T / 41 220).

These patents also show that the sulfonyl carbamide derivatives are excellent herbicidal activity against numerous monocotyledonous plants genes and dicotyledons, especially broad-leaved genes and grassy weeds (Green, J.M., Harrold J.E., Long J.D., Levitt G., Fitzgerald D.J .: Proc. S. Weed Sci. Soc. 34 214 [1981]), especially in Wheat and barley crops, (Hungarian Publication No. T / 39 322). Your advantage is that they are in a very low dose, in general at a rate of 5-50 g / ha, already effective are. Their disadvantage is that they are in more or less, the crops damage. During their application in practice turned out to be with cereals with ears of corn acceptably selective, in maize and sunflower crops however, are highly phytotoxic, therefore theirs Anti-doping recommended for cereal plants, in the case of corn, however, inevitable.

In EP-PS No. 01 27 469, after sowing, described antidota before rising, which the wheat and millet from herbicide damage protect from the sulfonyl carbamide type. As the cheapest proved the 2 [(aminocarbonyl) aminosulfonyl] - methyl benzoate and its ammonium salt or the 3 - [(aminocarbonyl) aminosulfonyl] -  2-thiophene carboxylic acid methyl ester.

According to US Pat. No. 43 43 649, 2-chloro-N - [(4-methoxy-6-methyl-1,3,5-triazin-2-yl) aminocarbonyl] benzene sulfonamide can be used to increase the selectivity -, 2,5-dichloro-N - [(4-, 6-dimethoxy-pyrimidin-2-yl) aminocarbonyl] benzenesulfonamide and 2-carbomethoxy-N - [(4,6-dimethyl-pyrimidine- 2-yl) -aminocarbonyl] -benzenesulfonamide herbicides, the 1,8-naphthalic anhydride, the α - (cyano-methoxyimino) - benzacetonitrile and the N, N-diallyl-2,2-dichloroacetamide can be used with very good results.

During in-house research on lowering the damaging effect of the herbi ziden sulfonylcarbamide derivatives were directed found that the stick on one or both Substituted atoms substituted N- (dichloroacetyl) glycine amide derivatives successfully used to avoid phyto toxicity can be applied.

This knowledge led to the present Er finding. The invention therefore relates to a Active ingredient a sulfonyl carbamide derivative of the general Formula (I) - wherein

R ₁ for hydrogen, halogen atom, lower alkyl, lower alkoxy, -NO ₂ -, -CO ₂ R ₃ -, -CO-NH-OR ₄ -, -SO ₂ -NH-OR ₄ -, -OCF ₃ -Group, in which R ₃ and R ₄ stand for lower alkyl group, R ₂ for hydrogen, halogen atom, for an optionally substituted lower alkyl, lower alkoxy, -NCO-, -CN-, -NHCOOR ₅ -, -NHCOR ₅ -, -NR ₆ R ₇ group, in which R _{5 is} a lower alkyl group, R ₆ and R _{7 are} a hydrogen atom or a lower alkyl group,

stands,

X and Y are the same or different and represent hydrogen atom, lower alkyl, lower alkoxy, lower alkylthio group, halogen atom, alkyl or alkoxy group substituted by 1-3 halogen atoms, dialkylamino with lower alkyl groups, -NO ₂ group, and K for stands -

and as an antidote on one or both sticks Substituted atom-substituted N- (dichloroacetyl) glycine amide derivative of the general formula (II) - wherein

R ₈ and R _{9 are the} same or different and represent hydrogen, C _1-8 alkyl, C _2-8 alkenyl, C _5-6 cycloalkyl, benzyl, optionally substituted phenyl or together with the included a nitrogen atom represent a hexamethylene imino group,
with the condition that when R _{8 represents} hydrogen atom, R _{9 has} a meaning other than phenyl group, R _{10 represents} C _1-5 alkyl, C _2-5 alkenyl or benzyl group -

herbicidal composition.

Among the compounds of the general formula (I), those are preferred in which
R ₁ for hydrogen atom, halogen atom, C _1-3 -alkyl-, C _1-3 -alkoxy-, -NO ₂ -, -CO ₂ R ₃ -, -CO-NH-OR ₄ -, -SO ₂ -NH- OR ₄ -, -OCF ₃ group - in which R ₃ and R _{4 are} C _1-3 alkyl groups - R _{2 represents} hydrogen atom, halogen atom, C _1-3 alkyl group, which can be substituted by 1-3 halogen atoms , for C _1-3 -alkoxy-, -NCO-, -CN-, NHCOOR ₅ -, -NHCOR ₅ -, -NR ₆ R ₇ group - in which R _{5 is} a C _1-4 -alkyl group, R ₆ and R _{7 are} hydrogen atom or C _1-3 alkyl group - stands for, X and Y are identical or different from each other and represent hydrogen atom, C _1-3 alkyl, C _1-3 alkoxy, C _1-3 alkylthio group, Halogen atom, C _1-3 alkyl or alkoxy group substituted by 1-3 halogen atoms, di (C _1-3 alkyl) amino, -NO ₂ group, K is -CH or N.

Of the compounds of the general formula (II), preference is given to those in which R ₈ and R _{9 are} identical or different and are for hydrogen atom, C _1-8 alkyl, C _2-8 alkenyl, C _5-6 Cycloalkyl, benzyl group, further optionally represent phenyl group substituted by one or two C _1-3 alkyl groups and / or halogen atoms, R ₈ and R _{9 together} with the enclosed nitrogen atom can also form a hexamethylene-imino group, with the condition that when R _{8 represents} hydrogen atom, R _{9 has} a meaning other than phenyl group, R _{10 represents} C _1-5 alkyl, C _2-5 alkenyl or benzyl group.

The compounds can be a halogen atom Contain fluorine, chlorine, bromine or iodine atom.

The herbicidal composition according to the invention contains the compounds of the general formulas (I) and (II) in a total amount of 5-95% by mass and in a mass ratio of 1: 10-1: 350.

The most advantageous to use as an antidote ble compounds of the general formula (II) summarized in Table I below.  

Table I

This antidote, its manufacturing process and their use to reduce the phytotoxicity of the herbicidal thiocarbamate or chloroacet Anilide derivatives are open in the Hungarian T-35 471.

The herbicidal compositions according to the invention can be used in crop protection practice in the form of Emulsion concentrates (EC), wettable powders (WP), Granules (G), aqueous or oily suspensions be used. The manufacture of the Invention contemporary compositions is shown in the following examples len set out without changing the scope of protection these examples will be restricted.

Example 1 Production of a wettable powder composition ions (32.1 WP)

0.1% by mass of the active ingredient 1- (2-carbomethoxybenzenesulfonyl) -3- (4-methyl-6-methoxy-1,3,5-triazin-2-yl) carbamide, 32% by mass of antidote ( Compound No. 41 in Table I) and 29% by mass of synthetic silicate carrier (Zeolex 444), 28.9% by mass of silica carrier, 2% by mass of aliphatic sulfonic acid Na salt wetting agent (Netzer IS), 3% by mass Cresol formaldehyde condensate (dispersant 1494) and 5% by mass of sulfite liquor powder (dispersant) are homogenized in a laboratory ball mill and pre-ground, then finely ground in an Ultraplex mill of the Alpine 100 LU type. This gives a wettable powder composition which contains the active ingredient and the antidote in a total amount of 32.1% by mass and in a ratio of 1: 320.
Levitation in 1% concentration: 83%.
Moist sieve residue (in a 100-DIN sieve): 1.2%.

Example 2 Production of a wettable powder composition (40.5 WP)

0.5% by mass of the active ingredient chlorosulfuron [1- (2-chlorophenylsulfonyl) -3- (4-methoxy-6-methyl- 1,3,5-triazin-2-yl) carbamide], 40% by mass of antidotum (Compound No. 41 in Table I) and 15% by mass Zeolex 444 and 35 mass% silica carrier, 3 mass% Dispersant 1494, 2 mass% wetting agent Netzer IS and 4.5 mass% sulfite liquor powder are based on the in Example 1 described way homogenized and fine  ground. So you get a wettable powder compo sition, the active ingredient and the antidote in one Total amount of 40.5% by mass and in a ratio of 1:80 contains.

Example 3 Production of a wettable powder composition tion (64.4 WP)

0.4% by mass of the active ingredient 1- (2-carbomethoxy benzenesulfonyl) -3- (4,6-dimethyl-pyrimidin-2-yl) - carbamide, 64 mass% antidotum (compound no. 60 of Table I) and 10% by mass of Zeolex 444 and 16% by mass of silica, 2% by weight of wetting agent Netzer IS, 3 mass% dispersant 1494 and 4.6 mass% sulfite liquor powder (dispersant) in the manner described in Example 1 homogenized and finely ground. So you get one wettable powder composition containing the active ingredient and the antidote in a total amount of 64.4% by mass and contains in a ratio of 1: 160.

Example 4 Preparation of an emulsion concentrate (48.3 EC)

0.3% by mass of the active ingredient chlorosulfuron and 48 mass% antidotum (Compound No. 24 of Table I) are stirred with a mixture of 33.7 mass% Xylene and 10 mass% dimethylformamide dissolved. It 6.5% by mass of the emulsifier Emulsogen IP-400 and 1.5% by mass of the emulsifier Emulsogen EL-400 (Mixture of dodecylbenzene sulfonic acid Ca salt and Fatty acid polyglycol ester) is added, then the Filtered solution.  

So you get an emulsion concentrate that Active ingredient and the antidote in a total amount of Contains 48.3% by mass and in a ratio of 1: 160. The Emulsion stability is in 1% concentration, in CIPAC A and CIPAC D water, out after 2 hours records after 24 hours despite a minimal reversible cream formation well.

Example 5 Preparation of an emulsion concentrate (80.25 U)

0.25 mass% of the active ingredient 1- (carbomethoxy benzenesulfonyl) -3- (4,6-dimethylpyrimidin-2-yl) carba mid and 80 mass% antidotum (compound no. 43 of the Table I) are made with stirring in a mixture 8% by mass of xylene and 3.75% by mass of dimethylformamide added solves. There will be 6% by mass of the emulsifier Emulsogen IP-400 and 2% by mass of the emulsifier Emulsogen EL-400 added, then the solution filtered.

So you get an emulsion concentrate that Active ingredient and the antidote in a total amount of Contains 80.25% by mass and in a ratio of 1: 320.

Example 6 Preparation of an emulsion concentrate (61.5 EC)

1.5% by mass of the active ingredient 1- (2-carbomethoxy benzenesulfonyl) -3- (4-methyl-6-methoxy-1,3,5-triazine 2-yl) carbamide and 60% by mass of antidote (compound No. 59 in Table I) are stirred in a Mixture of 20% by mass of xylene and 10.5% by mass of dimethyl formamide dissolved. There are 7 mass% of the emulsifier using Emulsogen IP-400 and 1% by mass of the emulsifier added by means of EL-400, then the solution is filtered  riert.

An emulsion is obtained in this way concentrate containing the active substance and the antidote in a total of 61.5 mass% and in the ratio 1:40 contains.

Example 7 Preparation of a suspension (71.75 FW)

1.75% by mass of the active ingredient 1- (2-carbomethoxy benzenesulfonyl) -3- (4,6-dimethyl-pyrimidin-2-yl) - carbamide, 70% by mass of antidote (compound no. 60 of the Table I) and 1% by mass of synthetic silicate carrier (Zeolex 444) become homogeneous in a laboratory ball mill nized and pre-ground. The powder mixture is under Stirring in a mixture of 5% by mass of monoethylene glycol, 1% by mass of the wetting agent oleyl methyl tauride (Arkopon T powder), 4% by mass of the dispersant nonylphenol polyglycol ether (Arkopol N-090) and 11.25 mass% Suspended water, then fine in a laboratory bead mill ground. The pearls are separated and the Suspension 6% by mass 2% xanthan resin thickener solution (Rhodopol 23) added, then stirring homogenized.

In this way you get a suspension that the active substance and the antidote in a total amount of 71.75% by mass and in a ratio of 1:40.

Levitation in 1% concentration: 94.6%.

Example 8 Preparation of a suspension (40.5 FW)

0.5% by mass of the active ingredient chlorsulfuron,  40% by mass of antidote (compound no. 41 of the Table I) and 5% by mass of Zeolex 444 carriers Homogenized and pre-homogenized in a laboratory ball mill grind. The powder mixture is stirred in a Mixture of 10% by mass of monoethylene glycol, 2.5% by mass of Arkopon T wetting agent, 5.5% by mass of the dispersant Suspend using Arkopol N-090 and 28.5 mass% water dated, then finely ground in a laboratory bead mill. After separating the grinding media, the suspension 8% by mass 2% xanthan resin thickening solution added give, then homogenize with stirring.

In this way you get a suspension which combines the active ingredient and the antidote in one contains 40.5% by mass and in a ratio of 1:80.

Example 9 Preparation of a suspension (16.1 FW)

0.1% by mass of the active ingredient 1- (2-carbomethoxy benzenesulfonyl) -3- (4-methyl-6-methoxy-1,3,5-triazine 2-yl) carbamide, 16 mass% antidotum (compound No. 24 in Table I) and 10% by mass Zeolex 444- Carriers are homogenized in a laboratory ball mill and pre-ground. The powder mixture is stirred in a mixture of 15% by mass of monoethylene glycol, 3% by mass of Arkopon T wetting agent, 6% by mass of Arkopol N-090 dispersant and 39.9% by mass Water suspended, then in a laboratory bead mill finely ground.

After removing the grinding media Suspension 10% by mass 2% xanthan resin thickener Solution added, and it becomes homogeneous with stirring nized.  

A suspension is obtained which has the effect substance and the antidote in a total amount of 16.1 mass% and in a ratio of 1: 160 contains.

The biological effectiveness of the Invention according compositions is in the following Examples set out.

Example 10

In laboratory tests, 400 g of soil was weighed into planters lined with PVC film with a surface area of 0.8 dm ² . The Ge bound of the arable crumb was 46, its humus content 1.95%, its pH 5.7. 5 grains of maize of the Pi 3732 variety, 20 grains of granular millet millet of the Alföld-1 variety and 0.5 g / jar of millet were sown into this soil. The seeds were covered with 200 g soil. The herbicidal active ingredient chlorosulfuron was applied in amounts of 5 and 10 g / ha alone, furthermore in combination with 0.4, 0.8 and 1.6 kg / ha antidota (compounds No. 24, 41, 43, 59 and 60 of Table I) sprayed on the floor. The experiment was ended by measuring the green mass and the shoot length of the plants grown for 14 days. The average values of the four repetitions are summarized in Tables II and III.

As a control, some were untreated Plants, on the other hand one with the antidote of Code number R-25788 (N, N-diallyl-2,2-dichloroacetamide) prepared combination used.  

Table II

Table III

The results of Tables II and III show good that with the compositions according to the invention, the the active ingredient chlorsulfuron the general Formula (I) and as an antidote on one or both Nitrogen atoms substituted N- (dichloroacetyl) -  glycinamide derivatives of the general formula (II) in Ratio 1:40 - 1: 320 included, symptom-free, healthy corn and granular millet while using chlorosulfuron alone this the two crops in both effort quantities damaged.

Example 11

It was the experiment according to Example 10 performed, with the difference that instead Chlorsulfuron the active ingredient 1- (2-carbomethoxy-ben benzenesulfonyl) -3- (4-methyl-6-methoxy-1,3,5-triazine-2- yl) carbamide was used.

The measurement results are in Tables IV and V combined, for simplicity the active substance was provided with the code number OH-3.

Table IV

Table V

From the results of Tables IV and V is clearly visible that the on one or both Nitrogen atoms substituted N- (dichloroacetyl) - glycinamide derivatives of the general formula (II), with the active ingredient 1- (2-carbomethoxy-benzenesulfonyl) - 3- (4-methyl-6-methoxy-1,3,5-triazin-2-yl) carbamide combined in a ratio of 40: 1 - 320: 1, the damaging effect of crops Prevent active ingredient successfully. The effect this antidote approaches the effect of anti doping of herbicidal active ingredients of sulfonyl carbamide type recommended in U.S. Patent No. 4,343,649 Antidote of code number R-25788, in many cases  it even surpasses them.

Example 12

The experiment according to Example 10 was carried out with the difference that instead of chlorine sulfuron the active ingredient 1- (2-carbomethoxy-benzene sulfonyl) -3- (4,6-dimethylpyrimidin-2-yl) carbamide has been used.

The measurement results are in Tables VI and VII summarized, for the sake of simplicity the active substance received the code number OH-4.

Table VI

Table VII

From the results of Table VI is good can be seen that the on one or both N atoms substituted N- (chloroacetyl) glycinamide general formula (II) when used with the active ingredient 1- (2-carbomethoxy-benzenesulfonyl) -3- (4,6-dimethyl pyrimidin-2-yl) carbamide of the general formula (I), combined in a ratio of 40: 1 - 320: 1 be the damaging effect of the crop of the active ingredient successfully prevent.

The results of Table VII show that that the applied in a dose of 10 g / ha Active ingredient 1- (2-carbomethoxy-benzenesulfonyl) -3- (4,6- dimethylpyrimidin-2-yl) carbamide the corn and  Black millet crops on such a large scale harms that even with the well known and widespread antidote R-25788 no equivalent appropriate protection can be guaranteed.

With the compositions according to the invention, the contain the antidotes of the general formula (II), a slightly better result could be achieved.

Claims (3)

1. As an active ingredient sulfonyl carbamide derivatives and as an antidote glycinamide derivatives containing herbicidal composition, characterized in that it contains sulfonyl carbamide derivatives of the general formula (I) as active ingredient - wherein R _{1 represents} hydrogen atom, halogen atom, lower alkyl, lower alkoxy, -NO ₂ -, -CO ₂ R ₃ -, -CIO-NO-OR ₄ -, -SO ₂ -NH-OR ₄ -, -OCF ₃ -Group - in which R ₃ and R _{4 are} short-chain alkyl groups -, R ₂ for hydrogen atom, halogen atom, for an optionally substituted lower alkyl, lower alkoxy, -NCO-, -CN-, -NHCOOR ₅ -, -NHCOR ₅ - , -NR ₆ R ₇ group - in which R _{5 is} a lower alkyl group and R ₆ and R _{7 represent} hydrogen atom or lower alkyl group -, X and Y are identical or different from one another and represent hydrogen atom, lower alkyl, lower alkoxy, lower alkylthio group, halogen atom, lower alkyl or alkoxy group substituted by 1-3 halogen atoms, dialkylamino with lower alkyl groups, or -NO ₂ group, K represents CH or N - and as an antidote an N atom substituted on one or both nitrogen atoms - (Dichloroacetyl) glycinamide of the general formula (II) - whereinR ₈ and R _{9 are the} same or different from each other and represent hydrogen atom, C _1-8 alkyl, C _2-8 alkenyl, C _5-6 cycloalkyl, benzyl, optionally substituted phenyl group or together with the enclosed nitrogen atom form a hexamethylene imino group,
with the condition that when R ₈ is hydrogen atom, R _{9 has} a meaning other than phenyl group, R _{10 is} C _1-5 alkyl, C _2-5 alkenyl or benzyl group - contains. 2. Herbicidal composition according to claim 1, characterized in that it contains a sulfonylcarbamide derivative of the general formula (I) as active ingredient - in which R _{1 represents} hydrogen atom, halogen atom, C _1-3 alkyl-, C _1-3 alkoxy- , -NO ₂ -, -CO ₂ R ₃ -, -CO-NH-OR ₄ -, -SO ₂ -NH-OR ₄ -, -OCF ₃ group - wherein R ₃ and R _{4 are} C _1-3 alkyl groups are - R ₂ for hydrogen atom, halogen atom, C _1-3 -alkyl group, which can be substituted by 1-3 halogen atoms, C _1-3 -alkoxy-, -NCO-, -CN-, -NHCOOR ₅ -, -NHCOR ₅ -, -NR ₆ R ₇ group - in which R ₆ and R _{7 are} H or C _1-3 -alkyl, X and Y are the same or different and are hydrogen atom, C _1-3 -alkyl-, C _{1 -3-} alkoxy, C _1-3 alkylthio group, halogen atom, for a C _1-3 alkyl or alkoxy group substituted by 1-3 halogen atoms, di (C _1-3 alkyl) amino, -NO ₂ group stand, K stands for CH or N - and as an antidote an N- (dichloroacetyl) glycinamide of the general formula (II) which is substituted on one or both N atoms - in which R ₈ and R _{9 are} identical or different from each other for hydrogen atom, C _1-8 alkyl, C _2-8 alkenyl, C _5-6 cycloalkyl, benzyl group, furthermore for one optionally by one or two C _1-3 Alkyl groups and / or halogen atoms are substituted phenyl groups, or R ₈ and R _{9 can} also form a hexamethylene-imino group together with the enclosed nitrogen atom, on the condition that when R _{8 represents} hydrogen atom, R _{9 has} a different meaning than phenyl group, R _{10 represents} C _1-5 alkyl, C _2-5 alkenyl or benzyl group. 3. Herbicidal composition according to claim 1, characterized in that it ver bonds of the general formulas (I) and (II) in a total concentration of 5-95% by mass and Ratio 1: 20-1: 350 contains.