WO1998041089A1

WO1998041089A1 - Novel herbicides

Info

Publication number: WO1998041089A1
Application number: PCT/EP1998/001431
Authority: WO
Inventors: Elmar Kerber; Willy Rüegg
Original assignee: Novartis Ag; Novartis-Erfindungen Verwaltungsgesellschaft Mbh
Priority date: 1997-03-14
Filing date: 1998-03-12
Publication date: 1998-09-24
Also published as: AU7427298A

Abstract

The invention concerns a method of combating undesired plant growth in cereal cultivation, characterized in that an active substance of formula (I), in which X is halogen and Y is -S(O)mR or a radical of formula (i), in which R is C1-C4 alkyl or C2-C4 alkenyl, Z is a direct chemical bond or CH2 and m is 0.1 or 2, m being 0 when R is C2-C4alkenyl, or a salt of the compound of formula (I) or an agent containing these active substances in a herbicidally active amount is applied to the plants or their habitat.

Description

New herbicides

The present invention relates to a new method for controlling weeds in crops, in particular crops of cereals.

The present invention thus relates to a process for controlling unwanted plant growth in cereals, characterized in that an active ingredient of the formula I

wherein X is halogen and

Y is -S (O) mR or a radical of the formula in which R dC -

Alkyl or C ₂ -C alkenyl, Z is a direct chemical bond or CH ₂ and m is 0.1 or 2, where m is 0 when RC ₂ -C ₄ alkenyl, or a salt of the compound of the formula I or an agent containing these active ingredients is applied in a herbicidally effective amount to the plants or their habitat.

The cyclohexanedione herbicides of the formula I used according to the invention and their preparation are described, for example, in JP 8-136464.

The invention also encompasses the use of salts which the compounds of the formula I can form with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases.

Among the alkali and alkaline earth metal hydroxides as salt formers, the hydroxides of lithium, sodium, potassium, magnesium or calcium should be emphasized, but especially those of sodium or potassium. As examples of suitable for ammonium salt formation amines include both ammonia as well as primary, secondary and tertiary CrCiβ-alkylamines, Cι-C ₄ hydroxyalkylamines and C ₂ -C ₄ -Alkoxyalkylamine into consideration, for example, methylamine, ethylamine, n-propylamine, iso-propylamine , the four isomeric butylamines, n-amylamine, iso-amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methyl-ethylamine, methyl-iso-propylamine, methyl-hexylamine, methyl-nonylamine, Methyl-pentadecylamine, methyl-octadecylamine, ethyl-butylamine, ethyl-heptylamine, ethyl-octylamine, hexyl-heptylamine, hexyl-octylamine, dimethylamine, diethylamine, di-n-propylamine, di-iso-propylamine, di-n-butylamine, Di-n-amylamine, di-iso-amylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, iso-propanolamine, N, N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine, allylamine, n-butenyl-2- amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2- amine, di-butenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, tri-iso-propylamine, tri-n-butylamine, tri-iso-butylamine, tri- sec-butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines such as pyridine, quinoline, iso-quinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines such as, for example, anilines, methoxyaniiines, ethoxyanilines, o, m, p-touidines, phenylenediamines, benzidines, naphthylamines and o, m, p-chloroaniiines; but especially triethylamine, iso-propylamine and di-iso-propylamine.

Compounds of the formula I are preferably used in which X is bromine and Y is -SCH ₃ .

The compounds summarized in Table 1 below can be mentioned as further preferred individual compounds from the scope of the formula I:

Table 1: Compounds of formula I.

Verb No. Y

1.01 Cl SCH ₃

1.02 Br SCH ₃

1.03 Cl SC ₂ H ₅

1.04 Br SC ₂ H ₅

1.05 Cl SnC ₃ H ₇

1.06 Br SnC ₃ H ₇

1.07 Cl SiC ₃ H ₇

1.08 Br SiC ₃ H ₇

1.12 Br S-CH ₂ CH = CH ₂

For the use according to the invention of the compounds of the formula I or compositions containing them, all the customary agricultural application methods, such as, for example, pre-emergence application, post-emergence application and seed dressing, and various methods and techniques, such as, for example, the controlled release of active substance, are suitable. The postemergent application is of particular importance. For this purpose, the active ingredient is drawn up in solution onto mineral granulate carriers or polymerized granules (urea / formaldehyde) and dried. If necessary, a coating can also be applied (coating granules), which allows the active ingredient to be dispensed in doses over a certain period of time.

The compounds of formula I can be used in unchanged form, i.e. as they are obtained in the synthesis, but are preferably processed in the usual way with the auxiliaries customary in formulation technology, e.g. to emulsifiable concentrates, directly sprayable or dilutable solutions, diluted emulsions, wettable powders, soluble powders, dusts, granules or microcapsules. The application methods, such as spraying, atomizing, dusting, wetting, scattering or pouring, are chosen in the same way as the type of agent, the intended goals and the given conditions.

The formulations, i.e. The agents, preparations or compositions containing the active ingredient of the formula I or at least one active ingredient of the formula I and generally one or more solid or liquid formulation auxiliaries are prepared in a known manner, e.g. by intimately mixing and / or grinding the active ingredients with the formulation auxiliaries, e.g. Solvents or solid carriers. Furthermore, surface-active compounds (surfactants) can also be used in the preparation of the formulations.

Possible solvents are: Aromatic hydrocarbons, preferably fractions C ₈ to C _12), such as xylene mixtures or substituted naphthalenes, phthalic esters such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols, and their ethers and esters such as Ethanol, ethylene glycol, ethylene glycol monomethyl or ethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or N, N-dimethylformamide, and optionally epoxidized vegetable oils such as epoxidized coconut oil or soybean oil; or water.

Natural rock flours, such as calcite, talc, kaolin, montmorillonite or attapulgite, are generally used as solid carriers, for example for dusts and dispersible powders. Can improve the physical properties of the formulation also highly disperse silica or highly disperse absorbent polymers can be added. Porous types such as pumice, broken brick, sepiolite or bentonite can be used as granular, adsorptive granulate carriers, and non-sorptive carrier materials such as calcite or sand. In addition, a large number of pregranulated materials of inorganic or organic nature, such as in particular dolomite or comminuted plant residues, can be used.

Depending on the nature of the active ingredient of formula I to be formulated, suitable surface-active compounds are nonionic, cationic and / or anionic surfactants and surfactant mixtures with good emulsifying, dispersing and wetting properties.

Suitable anionic surfactants can be both so-called water-soluble soaps and water-soluble synthetic surface-active compounds.

As soaps are the alkali, alkaline earth or optionally substituted ammonium salts of higher fatty acids (Cιo-C ₂₂ ), such as the Na or K salts of oleic or stearic acid, or natural fatty acid mixtures, for example from coconut or Tallow oil can be extracted. The fatty acid methyl taurine salts should also be mentioned.

However, so-called synthetic surfactants are used more frequently, in particular fatty alcohol sulfonates, fatty alcohol sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

The fatty alcohol sulfonates or sulfates are generally present as alkali, alkaline earth or optionally substituted ammonium salts and have an alkyl radical with 8 to 22 carbon atoms, alkyl also including the alkyl part of acyl radicals, for example the sodium or calcium salt lignin sulfonic acid, dodecyl sulfuric acid ester or a fatty alcohol sulfate mixture made from natural fatty acids. This subheading also includes the salts of sulfuric acid esters and sulphonic acids from fatty alcohol-ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and a fatty acid residue with 8-22 carbon atoms. Alkylarylsulfonates are, for example, the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or a naphthalenesulfonic acid / formaldehyde condensation product. Corresponding phosphates, such as, for example, salts of the phosphoric acid ester of a p-nonylphenol (4-14) ethylene oxide adduct or phospholipids, are also suitable.

Suitable nonionic surfactants are primarily polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which can contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols.

Further suitable nonionic surfactants are the water-soluble polyethylene oxide adducts containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups on polypropylene glycol, ethylene diaminopolypropylene glycol and alkyl polypropylene glycol with 1 to 10 carbon atoms in the alkyl chain. The compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Examples of nonionic surfactants are nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene-polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.

Fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate, are also suitable.

The cationic surfactants are primarily quaternary ammonium salts which contain at least one alkyl radical having 8 to 22 carbon atoms as N substituents and have low, optionally halogenated alkyl, benzyl or low hydroxyalkyl radicals as further substituents. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, e.g. the stearyl trimethyl ammonium chloride or the benzyl di (2-chloroethyl) ethyl ammonium bromide.

The surfactants commonly used in formulation technology, which can also be used in the agents according to the invention, are described, inter alia, in "Mc Cutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981, Stächen, H., "Tensid-Taschenbuch", Carl Hanser Verlag, Munich Vienna, 1981 and M. and J. Ash, "Encyclopedia of Surfactants", Vol III, Chemical Publishing Co., New York, 1980-81.

The herbicidal formulations generally contain 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of herbicide, 1 to 99.9% by weight, in particular 5 to 99.8% by weight, of a solid or liquid formulation auxiliary and 0 to 25% by weight, in particular 0.1 to 25% by weight, of a surfactant.

While concentrated products are preferred as a commodity, the end user generally uses diluted products.

The agents can also contain other additives such as stabilizers e.g. optionally epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soybean oil), defoamers, e.g. Contain silicone oil, preservatives, viscosity regulators, binders, adhesives as well as fertilizers or other active ingredients.

In particular, preferred formulations are composed as follows: (% = weight percent)

Emulsifiable concentrates:

Active ingredient: 1 to 90%, preferably 5 to 50% surfactant: 5 to 30%, preferably 10 to 20%

Solvent: 15 to 94%, preferably 70 to 85%

Dusts:

Active ingredient: 0.1 to 50%, preferably 0.1 to 1% solid carrier: 99.9 to 90%, preferably 99.9 to 99%

Suspension concentrates:

Active ingredient: 5 to 75%, preferably 10 to 50%

Water: 94 to 24%, preferably 88 to 30% surfactant: 1 to 40%, preferably 2 to 30% Wettable powders:

Active ingredient: 0.5 to 90%, preferably 1 to 80% surfactant: 0.5 to 20%, preferably 1 to 15% solid carrier material: 5 to 95%, preferably 15 to 90%

Granules:

Active ingredient: 0.1 to 30%, preferably 0.1 to 15% solid carrier: 99.5 to 70%, preferably 97 to 85%

The active compounds of the formula I are generally used successfully on the plant or its habitat at a rate of from 0.010 to 1 kg / ha, in particular from 0.010 to 0.5 kg / ha. The dosage required for the desired effect can be determined by experiment. It depends on the type of action, the stage of development of the crop and the weed, and on the application (place, time, method) and, depending on these parameters, can vary within wide ranges.

The compounds of the formula I are notable for herbicidal and growth-inhibiting properties which enable them to be used in crops of useful plants, in particular in cereals and particularly preferably in barley, and for non-selective weed control.

Cultures are also to be understood as those which have been made tolerant to herbicides or classes of herbicides by means of conventional breeding or genetic engineering methods. The weeds to be combated can be both mono- and dicotyledon weeds, such as Stellaria, Agrostis, Digitaria, Panicum, Brachiaria, Polygonum, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica. The following examples further illustrate the invention without restricting it.

Formulation examples for active ingredients of formula I (% = weight percent)

F1. Emulsion concentrates a) b) c) d)

Active ingredient acc. Table 1 5% 10% 25% 50%

Ca-dodecylbenzenesulfonate 6% 8% 6% 8%

Castor oil polyglycol ether 4% - 4% 4%

(36 moles of EO)

Octylphenol polyglycol ether - 4% - 2%

(7-8 mol EO)

Cyclohexanone - - 1 o% 20% Ό

Aroma. Hydrocarbon- 85% 78% 55% 16% Ό mixture C9-C ₁₂

Such concentrates can be used to prepare emulsions of any desired concentration by dilution with water.

F2. Solutions a) bb)) cc)) d)

Active ingredient acc. Table 1 5% 1 100 %% 5 500 %% 90%

1-methoxy-3- (3-methoxy-propoxy) propane 20% 20%

Polyethylene glycol MG 400 20% 10%.

N-methyl-2-pyrrolidone - - 30% 10%

Aroma. Hydrocarbon 75% 60% mixed C ₉ -C ₁₂

The solutions are suitable for use in the form of tiny drops. F3. Spray powder a) b) c) d)

Active ingredient acc. Table 1 5% 25% 50% 80%

Na lignin sulfonate 4% - 3% -

Na lauryl sulfate 2% 3% - 4%

Na diisobutyl naphthalenesulfonate - 6% 5% 6%

Octylphenol polyglycol ether - 1% 2% -

(7-8 mol EO)

Fumed silica 1% 3% 5% 10 ° /

Kaolin 88% 62% 35% -

The active ingredient is mixed well with the additives and ground well in a suitable grinder. Spray powder is obtained which can be diluted with water to form suspensions of any desired concentration.

F4. Coating granules a) b) c)

Active ingredient acc. Table 1 0.1% 5% 15% finely divided silica 0.9% 2% 2% anorg. Carrier material 99.0% 93% 83% (00.1 - 1 mm) such as CaCO ₃ or SiO ₂

The active ingredient is dissolved in methylene chloride, sprayed onto the carrier and the solvent is then evaporated off in vacuo.

F5. Coating granules a) b) c)

Active ingredient acc. Table 1 0.1% 5% 15% polyethylene glycol MG 200 1.0% 2% 3% finely divided silica 0.9% 1% 2% anorg. Backing material 98.0% 92% 80% (00.1 - 1 mm) such as CaCO ₃ or SiO ₂

The finely ground active ingredient is evenly applied in a mixer to the carrier material moistened with polyethylene glycol. In this way, dust-free coating granules are obtained.

F6. Extruder granules a) b) c))

Active ingredient acc. Table 1 0.1% 3% 5% 15% Na lignin sulfonate 1.5% 2% 3% 4% carboxymethyl cellulose 1.4% 2% 2% 2% kaolin 97.0% 93% 90% 79%

The active ingredient is mixed with the additives, ground and moistened with water. This mixture is extruded and then dried in an air stream.

F7. Dusts a) b) c)

Active ingredient acc. Tables 1 0.1% 1% 5%

Talc 39.9% 49% 35%

Kaolin 60.0% 50% 60%

Ready-to-use dusts are obtained by mixing the active ingredient with the carrier substances and grinding them in a suitable mill.

F8. Suspension concentrates a) b) c) d)

Active ingredient acc. Table 1 3% 10% 25% 50%

Ethylene glycol 5% 5% 5% 5%

Nonylphenol polyglycol ether - 1% 2% -

(15MOIEO)

Na lignin sulfonate 3% 3% 4% 5%

Carboxymethyl cellulose 1% 1% 1% 1% 37% aqueous formaldehyde- 0.2% 0.2% 0.2% 0.2%

solution

Silicone oil emulsion 0.8% 0.8% 0.8% 0.8%

Water 87% 79% 62% 38%

The finely ground active ingredient is intimately mixed with the additives. This gives a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.

Biolo examples

Example B1: Herbicidal action after emergence of the plants (post-emergence action)

Monocot and dicot test plants are grown in plastic pots under greenhouse conditions in standard soil. The test substances are applied in the 3- to 6-leaf stage of the test plants. The test substances are sprayed on in aqueous suspension (produced from a 25% wettable powder (example F3, b)) in accordance with the dosage of 500 to 60 g ai / ha (500 l water / ha). After application, the test plants are cultivated further in the greenhouse under optimal conditions. After a test period of 3 weeks, the test is evaluated with a nine-stage rating scale (1 = complete damage, 9 = no effect). Ratings of 1 to 4 (especially 1 to 3) mean a good to very good herbicidal action; Ratings of 6 to 9 (especially 7 to 9) show a good to very good tolerance in the crop.

It can be seen from the data compiled in the following tables B1 and B2 that the cyclohexanedione herbicides used according to the invention can selectively control weeds in barley crops.

Table B1 Verb. No. Application rates (g / ha)

1.02 500 250 125 60

Barley 8 9 9 9

Alopecurus 2 3 3 3

Avena 2 2 3 3

Amaranthus 3 3 3 3

Chenopodium 2 2 2 2

Polygonum 3 3 3 3

Sinapis 1 2 2 2

Stellaria 2 2 3 4 Galium 2 2 3 4

Table B2

Verb. No. Application rates (g / ha)

1.16 500 250 125 60

Barley 8 8 9 9

Alopecurus 3 3 4 5

Avena 3 4 4 7

Amaranthus 3 3 3 3

Chenopodium 3 3 3 3

Polygonum 2 2 2 4

Sinapis 2 2 2 2

Stellaria 2 2 2 3

Galium 2 2 3 4

The same results are obtained if the compounds of the formula I are formulated according to one of Examples F1 to F8.

Claims

Claims:

1. A method for controlling unwanted plant growth in crops of cereals, characterized in that an active ingredient of the formula I

wherein X is halogen and

Y is -S (O) mR or a radical of the formula in which RCC -

Alkyl or C ₂ -C ₄ alkenyl, Z is a direct chemical bond or CH ₂ and m is 0.1 or 2, where m is 0 if RC ₂ -C ₄ alkenyl, or a salt of the compound of the formula I or an agent containing these active ingredients is applied in a herbicidally effective amount to the plants or their habitat.

2. The method according to claim 1, characterized in that an amount of active ingredient from 0.010 to 1 kg / ha, in particular 0.010 to 0.5 kg / ha is applied.

3. Herbicidal and plant growth-inhibiting agent for use in the process according to claim 1, characterized in that it has, in addition to conventional inert formulation auxiliaries, a herbicidally active content of compound of the formula I or a salt of the compound of the formula I.

4. Composition according to claim 3, characterized in that it contains between 0.1% and 95% active ingredient of formula I.

5. Use of an agent according to claim 3 for combating undesirable plant growth in crops of cereals, especially barley.