DE3540919A1 - Herbicidal composition containing photosynthesis-inhibitor-type herbicides in combination with cyclic urea derivatives - Google Patents

Abstract

The novel synergistic active substance combinations composed of (1) a photosynthesis-inhibitor-type active substance (herbicide) and (2) a cyclic urea of the general formula (II) (synergist) <IMAGE> in which R<1> represents hydrogen or alkyl, R<2> represents alkyl and in each case optionally substituted cycloalkyl, phenyl or phenylalkyl, X represents oxygen or sulphur, -Y-Z- represents the groups <IMAGE> where R<3> represents hydrogen or alkyl, R<4> represents hydrogen or alkyl and R<2> and R<3> together can represent an alkylene bridge, have a particularly good herbidical activity. A typical example of the photosynthesis-inhibitor-type active substances is metribuzin.

Description

The present invention relates to new herbicidal synergistic Active ingredient combinations that are known from photosynthesis inhibitors Herbicides on the one hand and from certain partially known cyclic urea derivatives on the other hand.

It has been known that certain herbicides, such as B. 4-amino-6-tert-butyl-3-methylthio or -ethylthio-1,2,4-triazin-5-one; 1-amino-3- (2,2-dimethyl- propyl) -6- (ethylthio) -1,3,5-triazine-2,4-dione; 6-chlorine 2ethylamino-4-isopropylamino-1,3,5-triazine; 1-methoxy 1-methyl-3- (3,4-dichlorophenyl) urea; 1,3-dimethyl 1- (benzo-1,3-thiazol-2-yl) urea or 3-cyclohexyl 5,6-trimethyleneuracil, photosynthesis inhibiting properties own (see e.g. Carl Fedtke, Biochemistry and Physiology of Herbicide Action, Springer Verlag, 1982). A disadvantage of these herbicidal compounds however, that not all weeds and  Grasses are fully covered or that at accordingly high application rates of some crops to be partially damaged.

It was found that the new combinations of active ingredients consisting of
a) a photosynthesis inhibitor active ingredient (herbicide)
and
b) a cyclic urea derivative of the general formula (II) (synergist) in which
R ^{1 represents} hydrogen or alkyl,
R ^{2 represents} alkyl and also optionally substituted cycloalkyl, phenyl or phenylalkyl,
X represents oxygen or sulfur,
-YZ for the groupings stands where
R ^{3 represents} hydrogen or alkyl,
R ^{4 represents} hydrogen or alkyl
and
R ² and R ^{3 can} together represent an alkylene bridge,
have a particularly high herbicidal activity.

Surprisingly, the herbicidal activity of the Active ingredient combinations according to the invention essential higher than the sum of the effects of the individual active ingredients. In particular, the largely known cyclic urea derivatives of the general formula (II) with the usual application rates, no own herbicides Effect, but cause an increase in herbicides Efficacy of the photosynthesis inhibitor active ingredients. Consequently the synergistic effect found here is completely unexpected and surprising.

Since the synergistic effect also affects such weeds, by the photosynthesis inhibitors used Active ingredients when applied alone in the usual application rates insufficiently damaged or not at all are detected, represent the synergistic invention Active ingredient combinations are a valuable asset of technology.

As photosynthesis inhibitors for the inventive Drug combinations are preferably the following of the general formulas (I-A) to (I-J):  

(A) triazinone derivatives of the formula in which
X ^{1 represents} amino, optionally substituted alkylidene amino or alkyl having 1 to 2 carbon atoms;
X ^{2 represents} alkylthio having 1 to 2 carbon atoms, alkyl and dialkylamino each having 1 to 2 carbon atoms in each alkyl part or alkyl having 1 to 4 carbon atoms; and
X ^{3 represents} tert-butyl which is optionally substituted by halogen or phenyl which is optionally substituted.
(B) Triazinedione derivatives of the formula in which
X ^{4 represents} amino, optionally substituted alkylidene amino or alkyl having 1 to 2 carbon atoms;
X ^{5 represents} alkylthio having 1 to 2 carbon atoms, alkyl and dialkylamino each having 1 to 2 carbon atoms in each alkyl part or alkyl having 1 to 4 carbon atoms; and
X ^{6 represents} alkyl having 1 to 6 carbon atoms or optionally substituted phenyl.
(C) triazine derivatives of the formula in which
X ^{7 represents} chlorine, alkoxy or alkylthio, each having 1 to 2 carbon atoms;
X ^{8 represents} alkylamino with 1 to 4 carbon atoms in the alkyl part, and
X ^{9 represents} optionally substituted by cyano alkyl having 1 to 4 carbon atoms.
(D) Urea derivatives of the formula in which
X ^{10 represents} optionally substituted phenyl, benzthiazolyl or optionally substituted thiadiazolyl;
X ^{11 represents} hydrogen or methyl;
X ^{12 represents} methyl; and
X ^{13 represents} hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 2 carbon atoms or alkynyl having 2 to 4 carbon atoms.
(E) carboxanilide derivatives of the formula

in which
X ^{14 represents} alkyl having up to 6 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkenyl having 2 to 4 carbon atoms or cycloalkyl having 3 to 6 carbon atoms; and
X ^{15 represents} optionally substituted phenyl.
(F) uracil derivatives of the formula in which
X ^{16 represents} alkyl of 1 to 6 carbon atoms or cycloalkyl of 5 to 7 carbon atoms;
X ^{17 represents} halogen;
X ^{18 represents} alkyl having 1 to 2 carbon atoms, or
X ¹⁷ and X ¹⁸ together represent an optionally substituted alkylene chain or an optionally substituted fused benzene ring; and
X ^{19 represents} the CO or SO ₂ group.
(G) biscarbamate derivatives of the formula in which
X ^{20 represents} alkyl with 1 to 4 carbon atoms or optionally substituted phenyl; and
X ^{21 represents} alkoxy having 1 to 4 carbon atoms or dialkylamino having 1 to 2 carbon atoms in each alkyl part.
(H) pyridazinone derivatives of the formula in which
X ^{22 represents} optionally substituted phenyl;
X ^{23 represents} amino, alkylamino or dialkylamino, each having 1 or 2 carbon atoms in each alkyl part; and
X ^{24 represents} halogen.
(J) hydroxybenzonitrile derivatives of the formula in which
X ^{25 represents} halogen and
X ^{26 represents} halogen.

The following photosynthesis inhibitor active compounds of the general formulas (IA) to (IJ) are particularly preferred:
(A) Triazinone derivatives of the formulas (B) Triazinedione derivative of the formula (C) Triazine derivatives of the formulas (D) Urea derivatives of the formulas (E) carboxanilide derivatives of the formulas (F) Uracil derivatives of the formulas (G) biscarbamate derivatives of the formulas (H) Pyridazinone derivatives of the formulas (J) Hydroxybenzonitrile derivatives of the formulas

The photosynthesis inhibitor active ingredients of the formulas (I-A) to (I-J) are known (see, for example, Carl Fedtke, Biochemistry and Physiology of Herbicide Action, Springer- Verlag, 1982).

Formula (II) provides a general definition of the cyclic urea derivatives to be used as a mixture component. In this formula are preferably
R ^{1 represents} hydrogen or straight-chain or branched alkyl having 1 to 6 carbon atoms,
R ² for straight-chain or branched alkyl having 1 to 8 carbon atoms, for optionally mono- to trisubstituted, identically or differently substituted cycloalkyl with 5 to 7 carbon atoms (where halogen and alkyl with 1 to 4 carbon atoms are preferably mentioned as substituents), furthermore for each optionally substituted phenyl or phenylalkyl with 1 or 2 carbon atoms in the alkyl part (halogen or alkyl with 1 to 4 carbon atoms being mentioned as substituents),
X for oxygen or sulfur,
-YZ- for the groupings in which
R ^{3 represents} hydrogen or straight-chain or branched alkyl having 1 to 4 carbon atoms,
R ^{4 represents} hydrogen or straight-chain or branched alkyl having 1 to 4 carbon atoms,
and
R ² and R ³ together for a tetramethylene or trimethylene group.

Compounds of the formula (II) in which
R ^{1 represents} hydrogen or straight-chain or branched alkyl having 1 to 4 carbon atoms,
R ^{2 stands} for straight-chain or branched alkyl having 1 to 6 carbon atoms, for cyclopentyl or cyclohexyl which may be monosubstituted or disubstituted, identically or differently (where methyl, ethyl, fluorine and chlorine may be mentioned as substituents) and for phenyl or benzyl which is optionally substituted ( where chlorine, fluorine, methyl and ethyl are mentioned as substituents),
X represents oxygen or sulfur,
-YZ- for the groupings in which
R ^{3 represents} hydrogen or methyl and
R ^{4 represents} hydrogen or methyl
and
R ² and R ³ together represent a tetramethylene or a trimethylene group.

The cyclic urea derivatives of the formula (II) are largely known (see e.g. J. Chem. Soc., Perkin Trans. 1 (2), 219-21, 19; Synthesis (9), 641-2, 1977; J. Org. Chem., 48 (13) 2246-54, 1983; DE-OS 33 52 203; Chem. Ber. 103 (3), 766-76; 1970; Zh. Org. Kim., 14 (5), 1084-6, 1978; US-PS 3 46 11 133) or they can be obtained in the usual way such as B. by cyclization of the corresponding hydantoic acid in the presence of an acid (see also the preparation examples).

The weight ratios of the active ingredients in the new drug combinations can be found in relatively large Areas fluctuate. Generally account for one Part by weight of photosynthesis inhibitor active ingredient (herbicidal Active ingredient) 0.25 to 100, preferably 5 to 50, in particular  10 to 20 parts by weight of cyclic urea derivative of formula (II) (synergist).

The photosynthesis inhibitor active ingredients have strong herbicides Effects on. Still, they own against some Weeds such as B. Galium aparine, Iopmoea hederacea, Datura stramonium, Cirsium arvense, Convolvulus arvensis or Solanum nigrum and some grasses, such as. B. Agropyron repens, Avena fatua, Cynodon dactylon, Cyperus ssp. and Lolium rigidum not always sufficient Effect. The active ingredient combinations according to the invention extend the spectrum of action of the compounds of the formulas (I-A) to (I-J) and thereby enable control this by the herbicidal active ingredients alone weeds that are difficult or impossible to control.

The active compound combinations according to the invention can e.g. B. can be used in the following plants:

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, ipomoea, polygonum, sesbania, ambrosia, cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea.

Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cuburbita.

Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.

Monocot cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium.

The use of the active compound combinations according to the invention is by no means limited to these genera, but also extends in the same way on other plants.

The active compound combinations according to the invention show in particular in addition to a good effect against grassy (Monocot) weeds also have a good herbicidal effect in broad-leaved (dicotyledon) weeds.  

(The cyclic to be used according to the invention as synergists Urea derivatives (II) show in corresponding Application rates or concentrations also fungicidal activity such as especially against Oomycetes and Pyricularia oryzae on rice. In addition, show the invention Synergists have a root systemic effect in the Use as nematicides.)

The active compound combinations according to the invention can be in the customary formulations, such as solutions, Emulsions, wettable powders, suspensions, powders, dusts, Pastes, soluble powders, granules, suspension Emulsion concentrates, active ingredient-impregnated nature and synthetic materials and very fine encapsulation in polymers Fabrics.

These formulations are prepared in a known manner e.g. B. by mixing the active ingredients with extenders, So liquid solvents and / or solid Carriers, optionally using surfactants Agents, i.e. emulsifiers and / or Dispersing agents and / or foaming agents.

In the case of the use of water as an extender e.g. B. also organic solvents as auxiliary solvents be used. As a liquid solvent essentially come into question: aromatics, such as xylene, Toluene, or alkylnaphthalenes, chlorinated aromatics or  chlorinated aliphatic hydrocarbons, such as chlorobenzenes, Chlorethylene or methylene chloride, aliphatic Hydrocarbons, such as cyclohexane or paraffins, e.g. B. petroleum fractions, mineral and vegetable oils, Alcohols, such as butanol or glycol, and their ethers and Esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water.

The following are suitable as solid carriers:
e.g. B. natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silica, aluminum oxide and silicates, are suitable as solid carriers for granules: z. B. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; as emulsifying and / or foam-generating agents come into question: z. B. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for. B. alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as dispersants come into question: z. B. lignin sulfite and methyl cellulose.

In the formulations, adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers can be used, such as Gum arabic, polyvinyl alcohol, polyvinyl acetate, as well natural phospholipids such as cephalins and lecithins and synthetic phospholipids. Other additives can be mineral and vegetable oils.

Dyes can be used as additional additives in the formulations such as inorganic pigments, e.g. B. iron oxide, titanium oxide, Ferrocyan blue and organic dyes, such as alizarin, Azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, Molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 weight percent active ingredient combination, preferably between 0.5 and 90%.

The active compound combinations according to the invention are in general in the form of ready-to-use formulations brought. The contained in the active ingredient combinations Active ingredients can also be used as individual formulations mixed application, d. H. in the form of tank mixes be applied.  

The new drug combinations can be used as such or in their formulations also in a mixture with other known ones Find herbicides for weed control, where again ready formulations or tank mixes possible are. A mix with others known active ingredients, such as fungicides, insecticides, Acaricides, nematicides, bird repellants, Growth substances, plant nutrients and soil structure improvers is possible.

As such, the new active ingredient combinations can be used in Form of their formulations or from them by further Dilute prepared forms of use, such as ready-to-use Solutions, suspensions, emulsions, powders, pastes and granules are used. The application happens in the usual way, e.g. B. by pouring, spraying, spraying, Scatter.

The active compound combinations according to the invention can both before and after sowing as well as after emergence of the plants together or in separate applications be applied. Here the order plays the application does not matter.

When using the synergists according to the invention, the usual application rate of the herbicides of the formulas (I-A) to (I-J) can be reduced. The application rate of herbicidal Photosynthesis inhibitor active ingredient lies in surface treatment  between 0.01 and 3.0 kg / ha, preferably between 0.05 and 2.0 kg / ha. The application rate of synergistic cyclic Urea derivative lies in surface treatment between 0.1 and 10 kg / ha, preferably between 0.5 and 3 kg / ha.

The good herbicidal activity of the active compound combinations according to the invention goes from the examples below forth. While the individual active ingredients in the herbicidal The combinations show an effect weaknesses Weed action via a simple action summation goes out.

Herbicides always have a synergistic effect before if the herbicidal effect of the active ingredient combination is greater than the sum of the effects of the applied Active ingredients.  

Examples of use: Example A Pre-emergence test

Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

For the preparation of a suitable active ingredient preparation is mixed 1 part by weight of herbicidal active ingredient or Synergists or a mixture of herbicidal active ingredient and synergists with the specified amount of solvent, adds the specified amount of emulsifier and dilutes the concentrate with water to the desired concentration.

Seeds of the test plants are sown in normal soil and watered after 24 hours with a herbicide preparation or with the synergist preparation or with the preparation from synergists and herbicidal active ingredient. The amount of water per unit area is expediently kept constant. The concentration of active substance in the preparation is irrelevant, the only decisive factor is the amount of active substance applied per unit area. After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control. It means:
0% = no effect (like untreated control)
100% = total annihilation

Active ingredients, application rate and results are shown in the following Tables.  

Pre-emergence test

Table A ₁

Synergistic effect of cyclic urea derivatives (II) (= synergist S) and 4-amino-6-tert-butyl-3-methylthio-1,2,4-triazin-5-one (IA-1) (= herbicide H) to Ipomoea hederacea. The application rate in kg / ha relates to the active ingredient content.

Table ₁ A sequel

Table ₁ A sequel

The sole use of the herbicide (I-A-1) in one Concentrations of 0.5 and 2.0 kg / ha lead to Ipomoea hederacea to damage of 80 or 95%.  

Manufacturing examples example 1

100 g (10.5 mol) of 5-cyclohexylhydantoic acid with 100 ml of concentrated hydrochloric acid and 500 ml Refluxed ethanol for 8 hours and then cooled down. The precipitated product is suctioned off, washed with water, dried and from ethanol recrystallized.

55 g (60% of theory) of 3-cyclohexylhydantoin are obtained as white crystals with a melting point of 169-171 ° C.  

Manufacture of the starting product

75 g (1 mol) of glycine are mixed in a mixture of 500 ml 2N sodium hydroxide and 500 ml of acetone submitted and under gentle cooling dropwise with 125 g (1 mol) of cyclohexyl isocyanate transferred. The mixture is stirred for 2 hours and then with semi-concentrated hydrochloric acid adjusted to pH 3. The failing product is suctioned off, washed with water and dried.

176 g (88% of theory) of 5-cyclohexylhydantoic acid are obtained melting point 160-162 ° C.

The compounds of the general formula (II) can be obtained (see Table 1).

Table 1

Table 1 continued

Table 1 continued

Claims (8)

1. Herbicidal agents, characterized by a content of an active ingredient combination consisting of
(a) a photosynthesis inhibitor active ingredient (herbicide) and
(b) a cyclic urea derivative of the general formula (II) (synergist) in which
R ^{1 represents} hydrogen or alkyl,
R ^{2 represents} alkyl and also optionally substituted cycloalkyl, phenyl or phenylalkyl,
X represents oxygen or sulfur
-YZ- for the groupings stands where
R ^{3 represents} hydrogen or alkyl and
R ^{4 represents} hydrogen or alkyl
and
R ² and R ³ together can represent an alkylene bridge. 2. Herbicidal compositions according to claim 1, characterized in that they contain as photosynthesis inhibitor active ingredients (herbicides) compounds from the active ingredient groups of the formulas (IA) to (IJ) mentioned below:
(A) triazinone derivatives of the formula in which
X ^{1 represents} amino, optionally substituted alkylidene amino or alkyl having 1 to 2 carbon atoms,
X ^{2 represents} alkylthio having 1 to 2 carbon atoms, alkyl- and dialkylamino each having 1 to 2 carbon atoms in each alkyl part or alkyl having 1 to 4 carbon atoms, and
X ^{3 represents} tert-butyl which is optionally substituted by halogen or optionally substituted phenyl,
(B) Triazinedione derivatives of the formula in which
X ^{4 represents} amino, optionally substituted alkylidene amino or alkyl having 1 to 2 carbon atoms,
X ^{5 represents} alkylthio having 1 to 2 carbon atoms, alkyl and dialkylamino each having 1 to 2 carbon atoms in each alkyl part or alkyl having 1 to 4 carbon atoms, and
X ^{6 represents} alkyl having 1 to 6 carbon atoms or optionally substituted phenyl.
(C) triazine derivatives of the formula in which
X ^{7 represents} chlorine, alkoxy or alkylthio, each having 1 to 2 carbon atoms,
X ^{8 represents} alkylamino with 1 to 4 carbon atoms in the alkyl part, and
X ^{9 represents} optionally substituted by cyano alkyl having 1 to 4 carbon atoms.
(D) Urea derivatives of the formula in which
X ^{10 represents} optionally substituted phenyl, benzthiazolyl or optionally substituted thiadiazolyl;
X ^{11 represents} hydrogen or methyl;
X ^{12 represents} methyl; and
X ^{13 represents} hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 2 carbon atoms or alkynyl having 2 to 4 carbon atoms,
(E) carboxanilide derivatives of the formula in which
X ^{14 represents} alkyl having up to 6 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkenyl having 2 to 4 carbon atoms or cycloalkyl having 3 to 6 carbon atoms, and
X ^{15 represents} optionally substituted phenyl,
(F) uracil derivatives of the formula in which
X ^{16 represents} alkyl having 1 to 6 carbon atoms or cycloalkyl having 5 to 7 carbon atoms,
X ^{17 represents} halogen,
X ^{18 represents} alkyl having 1 to 2 carbon atoms, or
X ¹⁷ and X ¹⁸ together represent an optionally substituted alkylene chain or an optionally substituted fused benzene ring, and
X ^{19 represents} the CO or SO ₂ group.
(G) biscarbamate derivatives of the formula in which
X ^{20 represents} alkyl with 1 to 4 carbon atoms or optionally substituted phenyl; and
X ^{21 represents} alkoxy having 1 to 4 carbon atoms or dialkylamino having 1 to 2 carbon atoms in each alkyl part.
(H) pyridazinone derivatives of the formula in which
X ^{22 represents} optionally substituted phenyl,
X ^{23 represents} amino, alkylamino or dialkylamino, each having 1 or 2 carbon atoms in each alkyl part, and
X ^{24 represents} halogen, and
(J) hydroxybenzonitrile derivatives of the formula in which
X ^{25 represents} halogen and
X ^{26 represents} halogen. 3. Herbicidal compositions according to claim 1, characterized in that they are 4-amino-6-tert-butyl-3-methylthio-1,2,4-triazin-5-one of the formula (IA) as a photosynthesis inhibitor active ingredient (herbicide) -1) (metribuzin) contain. 4. Herbicidal compositions according to claim 1, characterized in that in the drug combination the weight ratio of (1) photosynthesis inhibitor active ingredient (Herbicide) to (2) the cyclic urea derivative of formula (II) (synergist) between 1: 0.25 and 1: 100. 5. Use of active ingredient combinations according to claims 1 to 4 to control weeds. 6. Process for the preparation of herbicidal compositions, thereby characterized in that an active ingredient combination according to claims 1 to 4 with extenders and / or surfactants mixed. 7. Use of cyclic urea derivatives of the formula (II) according to claim 1 as synergists in combination with photosynthesis inhibitor herbicides.   8. Use of cyclic ureas of the formula (II) according to claim 1 as synergists in combination with the herbicidal active ingredient 4-amino-6-tert-butyl-3- methylthio-1,2,4-triazin-5-one (metribuzin) of the formula (I-A-1) according to claim 3.