JP3464608B2 - Herbicides and methods for controlling weeds - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel herbicide containing a composite active substance for weeding, which is suitable for selective weed control in the cultivation of useful plants such as rice cultivation. The invention further relates to a method for controlling weeds in the cultivation of useful plants, and the use of new agents for this purpose.

[0002]

Compounds of formula Ia

[Chemical 8]

And a compound of formula Ib

[Chemical 9]

Has a herbicidal effect, which is described, for example, in International Patent WO 91/05781, European Patent EP-A-0 768 034 and Pesticides Manual, 10th Edition, The British Crop Protection Co.
uncil, pp. 828-829. Formulas IIa to II listed below
The sulfonylureas of e are also known as herbicides:

Compounds of formula IIa:

[Chemical 10] Pesticide Manual, 10th Edition, The British Crop Protectio
n Council, known from pages 85-87,

Compounds of formula IIb:

[Chemical 11] Pesticide Manual, 10th Edition, The British Crop Protectio
n Council, known from pages 56-57,

Compounds of formula IIc:

[Chemical 12] Pesticide Manual, 10th Edition, The British Crop Protectio
n Council, pages 211-212,

Compounds of formula IId:

[Chemical 13] Pesticide Manual, 10th Edition, The British Crop Protectio
n Council, pp. 873-874,

Compounds of formula IIe:

[Chemical 14] Pesticide Manual, 10th Edition, The British Crop Protection
Known from Council, pp. 589-590.

In view of what has been shown here, it is surprising that when at least three active substances are combined in varying amounts, ie the active substances of the formulas Ia and Ib have the formula IIa mentioned above, When at least one of the active substances of IIb, IIc, IId and IIe is combined, the herbicidal effect is expanded, and most of the weeds mainly generated when useful plants are cultivated are germinated in the same manner as the pre-emergence treatment method. It is also controlled by the subsequent treatment method and practically useful plants are not damaged. Therefore, according to the present invention, a novel herbicide for selective weed control is proposed, which is a conventional herbicide, in addition to an inactive formulation aid, as an active substance,

On the other hand, the compound of formula Ia:

[Chemical 15]

And a compound of formula Ib

[Chemical 16]

And on the other hand, the formula IIa,

[Chemical 17]

And / or formula IIb,

[Chemical 18]

And / or formula IIc,

[Chemical 19]

And / or formula IId,

[Chemical 20]

And / or formula IIe

[Chemical 21] A herbicidally effective amount of at least one active substance of the formula: or salts of at least one compound of the formulas IIa to IIe, mixed with one another.

Quite surprisingly, the formulas Ia and Ib
Of the active substances of IIa, IIb, IIc, IId and / or IIe
By combining at least one of the active substances mentioned above, an effect more than the effect expected in principle can be obtained on the weeds to be weeded, and as a result, the action boundary between the two active substances, especially 2 It can be broadened in one perspective: Ia, Ib and IIa-IIe, which on the one hand show a certain good effect
The amount of individual active substances used is reduced.

On the other hand, the agents of the invention serve the purpose of controlling weeds, which exhibit a higher grade, where the individual substances have not been used in agriculture in their low dose range. This substantially widens the weeding spectrum,
This results in a concomitant increase in selectivity, especially for the cultivation of useful plants, which is necessary and desirable when the amount of active substance used is unintentionally high. Further, the agent according to the present invention enables the flexibility of the subsequent cultivation to be further increased while maintaining the excellent performance of controlling useful plants as weeds.

The mixed herbicides according to the invention are used against a large number of agriculturally important weeds, including chickweed,
Dutch Pepper, Nubabo, Mexican Starfish, Oat Grass, Millet, Mustard, Dougumugi, Eggplant, Safflower Bean, Hiet, Futoi, Water mallow, Modus, Indigo, Suzumenotepowou, Seibanmorokoshi, Ushinosipei, Cyperus vulgaris, Steller's seaweed, Steller's seaweed, Steller's seaweed, Steller's seaweed , Shungiku, Yaemgra, Violets, Acne, Azegaya, Scutellaria, Harry, American eel, Scutellaria, Astragalus, Sedum, Acacia, Clover, Clover, Platypus, Sayanukagusa, Kusanemushi, Inunoguri. Of particular note is the surprisingly rapid effect in the genus Echinococcus with the compounds of formula Ib in the mixed herbicides of the invention. Therefore, the mixed herbicides of the invention are particularly suitable for controlling the genus Echinochloa on weeds.

The agents of the invention are suitable for all spraying systems commonly used in agriculture, for example for pre-growth, post-growth and germination acceleration. The mixed herbicides of the invention are suitable for controlling weeds when cultivating useful plants such as various cereals, oilseed rape, sugar beet, sugar cane, farm cultivars, rice, corn and soybean, and non-selective weeds. Have The use of the mixed herbicides of the invention with particular preference is for weed control in rice (transplanting and sowing, prioritizing transplantation). Regarding cultivation, it should be understood that there are cultivations which have become resistant to the herbicide or herbicide class by the conventional culture method or genetic engineering method.

The invention likewise includes agriculturally compatible salts, wherein the compounds of formulas IIa to IIe form salts with amines, alkali metal bases and alkaline earth metal bases or quaternary ammonium bases. be able to. Lithium, sodium, potassium, magnesium or calcium hydroxides are prominent as the salt-forming agent in the alkali metal hydroxides and alkaline earth metal hydroxides, and particularly sodium or potassium hydroxides are mentioned.

Examples of suitable amines for the formation of ammonium salts include ammonia and primary, secondary and tertiary C ₁ -C ₁₈ -alkylamines, C ₁ -C ₄ -hydroxyalkylamines and C. _2- C ₄ -Alkoxyalkylamines come into consideration, for example the four isomers of methylamine, ethylamine, n-propylamine, isopropylamine, butylamine, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine. , Nonylamine, decylamine, pentadecylamine, hexadecylamine,

Heptadecylamine, octadecylamine, methyl-ethylamine, methyl-isopropylamine, methyl-hexylamine, methyl-nonylamine,
Methyl-pentadecylamine, methyl-octadecylamine, ethyl-butylamine, ethyl-heptylamine, ethyl-octylamine, hexyl-heptylamine, hexyl-octylamine, dimethylamine, diethylamine, di-n-propylamine, di-isopropyl. Amine, di-n-butylamine, di-n-amylamine, di-isoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine,

N-Propanolamine, isopropanolamine, 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-isopropylamine, tri-n-butylamine, tri-isobutylamine, tri-s-butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine. There is

Heterocyclic amines include, for example, pyridine, quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine.
Examples of primary arylamines include aniline, methoxyaniline, ethoxyaniline, o, m, p-toluidine, phenylenediamine, benzidine, naphthylamine and o, m, p-chloroaniline, and especially triethylamine, isopropylamine. And di-isopropylamine are excellent. The combined active substances according to the invention contain the active substances of the formulas Ia and Ib in a specific mixing ratio. The preferred mixing ratio between the active substances of the formulas Ia and Ib lies between 0.8: 1.2 and 1.2: 0.8,
1: 1 is particularly preferable.

The preferred mixing ratio between the mutually mixing partners of the formulas IIa to IIe lies between 1: 100 and 100: 1, where 1:10 to 10: 1 are preferred. Formula Ia
And compounds of formula Ib are combined to form formulas IIa, IIb, IIc, IId
And / or the preferred mixing ratio with the compound of IIe is 1:
Lies between 100 and 100: 1, where 1:10 and 10: 1
However, 10: 1 to 1: 1 is particularly preferable. Formulas Ia and I
Particularly preferred mixing and mixing ratios when mixing the compound of b with the compounds of the formulas IIa to IIe are listed in Table 1.

[0028]

[Table 1] From these mixing ratios, the values given in Table 2 below are of particular interest.

[0029]

[Table 2] A particularly effective herbicidal mixed active substance of formula Ia
And a compound of formula Ia, IIc, IId or IIe has been demonstrated, wherein a mixing ratio of Ia to Ib of 1: 1 is preferred.

The variation of the amount of application is in a wide range, and it depends on the nature of the cultivated land, the method of application (pre-growth or post-growth treatment; seed sterilization; furrow application; non-arable land application, etc.), cultivated plant, and control. It depends on weeds, the prevailing climatic conditions in each case, and other factors that depend on the application method, application time and purpose of cultivation. In general, the mixed active substances according to the invention are added in an amount of 0.4 to 1 kg per hectare, mainly 0.4
~ 0.6 kg / ha can be sprayed.

Compounds of formula Ia and Ib and formulas IIa to IIe
The mixture of compounds of the above is used without changing its shape, that is, in the form obtained by synthesis, but it is preferred to treat by a conventional method, and a solvent, a solid carrier or a surfactant which is customary in the pharmaceutical technology is used. For example, it is used in a solution or a diluted solution which is directly sprayed, a dusting powder, a soluble powder, a fine granule, a granule or a microcapsule. The application methods, such as spraying, fumigation, atomization, wetting, dispersing or pouring, as well as the type of drug, are chosen according to the target and the given situation.

Formulations, Formulas Ia and Ib and Formula IIa
~ IIe active agents, and, if necessary, one or several pharmaceutical solids or liquid auxiliaries, pharmaceuticals, preparations or compositions prepared in a manner known per se,
For example, it is prepared by thorough mixing and / or milling of the active substances with formulation auxiliaries, for example solvents or solid carrier substances. Further, a compound having a surface activity (surfactant) can be additionally used when the preparation is carried out.

Substances which come into consideration as solvents are, for example, C ₈ -C such as xylene mixtures or substituted naphthalenes.
Aromatic hydrocarbons with preference for ₁₂ fractionated components, phthalic acid esters such as dibutyl phthalate, dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffin, alcohols and glycols, and their ethers and esters, namely ethanol, ethylene. Glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones such as cyclohexanone, N-methyl-2-pyrrolidone, dimethylsulfoxide or N, N-dimethylformamide and other strongly polar solvents, and, if necessary, Epoxidized vegetable oil such as epoxidized palm oil or soybean oil,
Or it is water.

As solid carrier materials, for example, for atomizing agents and for dispersing particles, generally natural rock powders are used, such as calcite, talc, kaolin, montmorillonite or attapulgite. Highly disperse silicic acid or highly dispersible and absorbable polymers can also be added to improve the physical properties of the formulation. As the carrier of the atomized adsorptive granule, for example, a porous type such as pumice, brick powder, sepiolite or bentonite is considered, and as the non-adsorptive carrier, for example, calcite or sand is considered. In addition, pregranulated, inorganic or organic natural substances, in particular dolomite or finely divided plant residues are used.

The surface-active compound may be a compound of formula Ia to be formulated.
And Ib, and nonionic, cationic and / or anionic surfactants and mixed surfactants, depending on the type of active substances of the formulas IIa to IIe, which have good emulsifying, dispersing and wetting properties. To be done. Suitable anionic surfactants include water-soluble soaps as well as water-soluble synthetic surface-active compounds. As the soap, higher fatty acid (C _{10 to} C
₂₂ ) Alkali metal salts, alkaline earth metal salts and optionally substituted ammonium salts, which are, for example, the Na or K salts of oleic acid or stearic acid, or Mention may be made of the alkali metal salts, alkaline earth metal salts and, if necessary, substituted ammonium salts of the natural fatty acid mixtures obtainable from coconut oil or tallow. In addition, fatty acid methyl taurine salts must be mentioned.

However, the most frequently used one is
They are so-called synthetic surfactants, in particular fatty alcohol sulfonates, fatty alcohol sulfates, sulfonated benzimidazole derivatives or alkylaryl sulfonates. The aliphatic alcohol sulfonate or the aliphatic alcohol sulfate is usually an alkali metal salt,
Alkaline earth metal salts, and optionally present as a substituted ammonium salt, have an alkyl residue having 8 to 22 carbon atoms, where alkyl includes the alkyl portion of the acyl residue. However, for example, Na salt or Ca of a fatty alcohol sulfate mixture made from lignin sulfonic acid, dodecyl sulfate or natural fatty acid.
It is salt.

Among the substances which belong to this are also sulfates of aliphatic alcohol-ethylene oxide adducts and salts of sulfonic acids. The sulfonated benzimidazole derivative has two sulfonic acid groups and 8 to 22 carbon atoms.
Preference is given to including one fatty acid residue with. The alkylaryl sulfonate is, for example, dodecylbenzene sulfonic acid, dibutyl naphthalene sulfonic acid, or Na of the naphthalene sulfonic acid-formaldehyde condensation product.
It is a salt, a Ca salt or a triethanolamine salt. Furthermore, for example, p-nonylphenol- (4-14)-
Corresponding phosphates, such as the phosphate salts of ethylene oxide-adducts, or phospholipids are also considered.

As nonionic surfactants, first of all, polyglycol ether derivatives of saturated or unsaturated fatty acids of aliphatic alcohols or cycloaliphatic alcohols and alkylphenols come into consideration, which are 3 to 30 glycol ether groups, and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon residue, and 6 to the alkyl residue of the alkylphenol.
It can contain 18 carbon atoms. Further suitable nonionic surfactants are water-soluble and have 20 to 25
0 ethylene glycol ether groups and 10-100
Polyethylene oxide-adduct containing 1 propylene glycol ether group, which is attached to polypropylene glycol, ethylene diamino polypropylene glycol and alkyl polypropylene glycol having 1 to 10 carbon atoms in the alkyl chain.

The compounds listed above usually contain 1 to 5 units of ethylene glycol to 1 unit of propylene glycol. Examples of nonionic surfactants include nonylphenol polyethoxyethanol, castor oil polyglycol ether, polypropylene-polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Furthermore, fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate, come into consideration.

In the case of cationic surfactants, quaternary ammonium salts are of particular concern, where the N-substituent contains at least one alkyl radical having 8 to 22 carbon atoms and other Substituents are lower, optionally halogenated, alkyl, benzyl or lower hydroxyalkyl residues. These salts are preferentially halides, methylsulfates or ethylsulfates, for example stearyltrimethylammonium chloride or benzyldi- (2-chloroethyl) -ethylammonium bromide.

The surfactants customary in the pharmaceutical art can also be used in the agents of the invention, but these are, inter alia, "Mc Cutcheon's Detergents and Emulsifiers Ann.
ual "MC Publishing Corp., Ridgewood New Jersey, 198
1, Stache, H., "Tensid-Taschenbuch", Carl Hanser V
erlag, Muenchen / Wien, 1981 and M. und J. Ash, "Enc
yclopedia of Surfactants ", VolI- III, Chemical Pu
Blishing Co., New York, 1980-81.

The herbicidal preparations are usually prepared by mixing the active substances consisting of the compounds of the formulas Ia and Ib and the compounds of the formulas IIa to IIe in an amount of 0.1 to 99% by weight, particularly 0.1 to 95% by weight, and solid or liquid formulation auxiliaries. 1 to 99.9% by weight, and surfactant
It contains 0 to 25% by weight, in particular 0.1 to 25% by weight. Concentrated drugs are usually given priority as commercial products, but end users usually use diluted drugs. The drug may also contain other additives, these include, for example:
Stabilizers such as epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soybean oil), defoamers such as silicone oils, preservatives, viscosity modifiers, binders, adhesives, and fertilizers if necessary. There are other active substances. A particularly preferred formulation consists of:

(% = Weight percent)

[Table 3]

The following examples illustrate the invention in more detail, but do not limit it.

[Table 4]

The following solutions are suitable for use in the form of fine drops.

[Table 5]

The active substance is well admixed with the additives and finely ground in a suitable mill. A spray powder is obtained, suspended in water and diluted to the desired concentration.

[Table 6]

The active substance is dissolved in methylene chloride, sprayed onto the carrier and the solvent is subsequently evaporated in a vacuum.

[Table 7]

The finely powdered active substance is uniformly coated on a carrier moistened with polyethylene glycol in a mixer. This method gives dust-free coated granules.

[Table 8]

The active substance is well mixed with the additives, pulverized and wetted with water. The mixture is extruded and subsequently dried in a stream of air.

[Table 9]

Propellants for spraying are obtained by mixing the active substance with a carrier substance and milling in a suitable mill.

[Table 10]

The finely divided active substance is thoroughly mixed with the additives. A suspension concentrate is thus obtained, which can be diluted with water to produce a suspension of the desired concentration.
The active substances of the formulas Ia and Ib and their mixed partners of the formula II
Compounds a, IIb, IIc, IId and IIe are individually formulated and then placed in a sparger prior to sprinkling in a “tank mixing method”
As a result, it is often more practical when mixed with water at the desired mixing ratio.

Biological Example: Grass plants are sown on the surface of a resin container containing standard soil, and then the soil surface is filled with water. Decimate rice after 14 days (depth 1c
m). Subsequently, weeds are sown on the surface of the resin container containing the standard soil, and then the soil surface is filled with water. Immediately thereafter, the test substance is introduced as an aqueous suspension by the inflow method (dispersion in water).
Disperse by. After spraying, raise the water level by 1 cm,
Furthermore, the test plants are grown under optimal conditions in a glass growth room, and the test results are evaluated 4 weeks after the application (the effect is expressed in%, 100% = plant death, 0% = no phytotoxic action).

Test Plants: Rice, Koshihikari Tainubie (ECHOR) Barnyardgrass (ECHCG) Vasebie (British) (ECHCO GB) Vasebie (Indonesia) (ECHCO IND) The results shown in Table 11 below were obtained.

[0054]

[Table 11]

As can be seen from Table 11, the compounds of formulas Ia and Ib, when used alone at the test doses,
Even if satisfactory weed control can be performed, it inhibits rice, which is a cultivated plant, by 10%. The compound of formula IIa has no phytotoxic effect on rice at the test application amount, but its herbicidal effect on weeds is unsatisfactory. On the other hand, the formula Ia,
The inventive admixture consisting of Ib and a compound of formula IIa has no phytotoxic effect on rice (0%) and completely kills all weeds tested (100% effect). Therefore, the admixture of the present invention exerts the effect of increasing the selectivity in controlling weeds in rice cultivation.

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Claims (8)

(57) [Claims] 1. In addition to inactive auxiliaries for pharmaceuticals, the active substance can also be represented by (A) the following formula Ia: And (B) the following formula Ib: And (C) the following formula IIa: And / or the following formula IIb: And / or the following formula IIc: And / or the following formula IId: And / or the following formula IIe: Of at least one active substance or formula (II
a) to (IIe), a herbicidally effective amount of a salt of at least one compound represented by the formula: mixed with each other. 2. A herbicide according to claim 1 which contains a compound of formula Ia and Ib and a herbicidally effective amount of a compound of formula IIa, IIc, IId or IIe. 3. The herbicide according to claim 1, wherein the mixing ratio of the compound of the formula Ia and the compound of the formula Ib is 1: 1. 4. An active substance of the combination of formulas Ia and Ib,
The herbicide according to claim 1, wherein the mixing ratio with the active substance of the formulas IIa, IIb, IIc, IId and / or IIe is 1: 100 to 100: 1. 5. The effective amount of herbicidal drug according to claim 1,
A method for controlling undesired plant growth in cultivating a useful plant, which comprises acting on a cultivated plant or a sphere thereof. 6. The method according to claim 5, wherein the useful plant is rice. 7. The method according to claim 5, which is used for controlling the genus Echinochloa. 8. The method according to claim 5, characterized in that useful plants are cultivated using the above-mentioned chemicals so that the sprayed amount per hectare corresponds to the total amount of the active substance of 0.4 to 1 kg.