JPH0489408A - Herbicide composition - Google Patents

Abstract

PURPOSE:To provide the subject composition exhibiting an excellent herbicidal activity which has not been predicted from the single property of each ingredient at a low dose and further having a wide herbicidal spectrum by combining a specific triazine derivative and a specified quinoline carboxylic acid herbicide. CONSTITUTION:A herbicide composition contains (A) a triazine derivative of formula I [A is a group of formula II (Z is O, S) or III (X<2> is methyl, F; (n) is 0-2); R<1> is H, methyl; <1> is F, Cl] [e.g. 2-amino-4-[1-(benzofuran-2'-yl)- ethylamino]-6-(alpha-fluoro, alpha-methylethyl)-s-triazine] and (B) a quinoline carboxylic acid herbicide of formula IV (R<2> is Cl, methyl) (e.g. 3,7-dichloroquinoline-8- carboxylic acid) as active ingredients. The combination of 2 kinds of the chemicals exhibits a synergistic activity, especially a remarkably high activity for gramineous crop upland fields. The combined chemicals have a large herbicidal activity against weeds but gives a little chemical damage to crops.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a herbicide composition containing a triazine derivative and a quinoline carboxylic acid herbicide as active ingredients.

[Prior Art and Problems to be Solved by the Invention] Various herbicides have been developed so far and have contributed to agricultural productivity and labor saving. However, as certain types of herbicides have been used for many years, the number of difficult-to-control weeds that these herbicides are not effective against has increased, and weed control that has a wide herbicide spectrum and is effective against these difficult-to-control weeds is becoming more and more common. It is hoped that a new drug will emerge. Furthermore, in order to solve the problem of environmental pollution caused by conventional herbicides, the development of highly active herbicides is also desired. Furthermore, in order to deal with the uneven emergence of weeds over a long period of time, we are developing a weed control method with excellent residual effect and a wide range of suitable treatment periods that are effective even when treated over a wide range of periods from before weed emergence to the growing season. The emergence of a drug is also awaited.

Under these circumstances, the present inventors discovered that a specific novel haloalkyl-containing triazine derivative has no chemical damage to grass field crops and has high herbicidal properties against difficult-to-control weeds in both soil and foliage treatments. It has been found that the compound is effective and has an excellent effect on treating flooded soil (Japanese Patent Application Nos. 1-38178 and 1-154465). The present inventors have conducted repeated studies to further improve the herbicidal activity of the triazine derivatives.

[Means to solve the problem]

As a result, a composition that combines the triazine derivative and a specific quinoline carboxylic acid herbicide exhibits excellent herbicidal activity that cannot be expected from the properties of each alone, and exhibits high herbicidal effects at lower dosages. They discovered that it has a wide herbicidal spectrum and completed the present invention.

That is, the present invention (wherein, X2 represents a methyl group or a fluorine atom, and n
represents an integer from 0 to 2. ), R1 represents a hydrogen atom or a methyl group, and Xl represents a fluorine atom or a chlorine atom. ] A triazine derivative represented by [wherein R2 represents a chlorine atom or a methyl group]. The present invention provides a herbicidal composition containing a quinolinecarboxylic acid herbicide represented by the following as an active ingredient.

Specific examples of the triazine derivative represented by the above general formula (I) include 2-amino-4-(1-(benzofuran-
2°-yl)ethylamino]-6-(α-fluoro, α
-Methylethyl) -S triazine 2-amino-4-CI-(benzothiophen-2-yl)ethylamino)-6-(α-fluoro.

α-methylethyl)-S-triazine 2-amino-4-(α-fluoro, α-methylethyl)
-6-(2-(3°,5°-dimethylphenoxy)-1
-methyl-ethylamino)-S-triazine2-amino-4-(1-(benzofuran-2yl)ethylamino)-6-(α-fluoroethyl)-s-)riazine2-amino-4-(α -Fluoro, α-methylethyl'
)-6-C2-(3°-fluorophenoxy)-1-methyl-ethylamino) -S-triazine 2-7mi/-
4-(α-chloro, α-methylethyl) -6-(2-
(3', 5°-dimethylphenoxy)-1-methylethylamino)-8-) riazine 2-amino-4-(α-ri4, α-methylethyl)
-6-(2-(3',5'-dimethylphenoxy)-1
-methyl-ethylamino)-S-) riazine, and the like.

The triazine derivative represented by the above general formula CI) can be produced by various methods. Among them, as an efficient manufacturing method, the general formula % formula % () [wherein A is the same as above. X4 represents a halogen atom.

] A salt of an alkylamine represented by H and the formula H2N-C-N
A by reacting cyanoguanidine represented by H-CN
-CH-NHCNHCNH2・HX' ・・
- [IV) [wherein A and X4 are the same as above. ] and then converting the alkyl biguanide salt to the general formula CH.

R'-C-C0OR'Xl...(V) [In the formula, R1 and Xl are the same as above. R4 has 1 carbon number
~4 alkyl group is shown. ] A method of reacting an alkyl ester represented by the following can be mentioned.

According to this, a salt of an alkylamine represented by the general formula CI) is reacted with cyanoguanidine to obtain a salt of an alkyl biguanide represented by the general formula (IV), which is then combined with an alkyl ester represented by the general formula (V). By the reaction, the desired triazine derivative represented by the general formula CI) can be efficiently obtained.

In the reaction between the salt of the alkylamine represented by the above general formula (II[) and cyanoguanidine, the recompound may be used in approximately equimolar proportions, and the solvent may be a cyclic hydrocarbon such as benzene, decalin, or alkylnaphthalene. , as well as carbon tetrachloride, ethylene dichloride, chlorobenzene,
Dichlorobenzene.

Chlorinated hydrocarbons such as trichlorobenzene and the like can also be used. Further, the reaction temperature is not particularly limited, and the reaction progresses satisfactorily at a temperature ranging from low to high temperatures, specifically in the range of 80 to 200°C.

Through this reaction, a salt of the alkyl biguanide derivative represented by the general formula (IV) is obtained, and by reacting this with an alkyl ester of the general formula (V), the desired general formula C
A triazine derivative represented by I) is produced. This reaction usually uses methanol.

Alcohols such as ethanol and isopropanol, various ketones, aliphatic hydrocarbons, and various ethers.

The process proceeds efficiently at about 10 to 100°C in the presence of a catalyst such as a base in a solvent such as various cyclic hydrocarbons or chlorinated hydrocarbons.

Furthermore, these compounds have optical isomers and are usually obtained as racemates, or each enantiomer can be obtained by known methods such as asymmetric synthesis.

In the present invention, it is possible to use either a racemic body or an optically heterocylindrical body alone. Furthermore, in the present invention, salts of inorganic acids or organic acids can also be used.

On the other hand, specific examples of the quinolinecarboxylic acid herbicide represented by the above general formula (I[) include 3,7-cycloquinoline-8-carboxylic acid and 7-methyl-3-chloroquinoline-8-carboxylic acid. can be mentioned. In addition,
3,7-cycloquinoline-8-carboxylic acid and 7-
Methyl-3-chloroquinoline-8-carboxylic acid is disclosed in JP-A-57-165368 and JP-A-59, respectively.
It can be produced by the method described in Japanese Patent No. 76061. These herbicides have a spectrum that also covers broad-leaved weeds in field crops, including grass weed Novie in paddy rice.

The herbicide composition of the present invention contains a triazine derivative represented by the above general formula CI) and a quinoline carboxylic acid herbicide represented by the above general formula [■] as active ingredients, but the blending ratio is particularly determined. There are no restrictions and excellent synergistic effects can be obtained in a wide range of blending ratios. Usually, triazine derivative: quinoline carboxylic acid herbicide = 10:1 to I:
It is preferable to mix within a range of 100 (weight ratio).

The herbicidal composition of the present invention comprises a triazine derivative represented by the above general formula CI) and a quinolinecarboxylic acid herbicide represented by the above general formula (I[) in a liquid carrier such as a solvent or a solid carrier such as mineral powder. Mix with wettable powders, emulsions, powders9
Granules, flowables.

It can be formulated and used in the form of a liquid or the like.

When formulating, emulsifier 9, dispersing agent, spreading agent,
Surfactants such as suspending agents, penetrating agents, and stabilizers.

Other adjuvants may be added.

When the herbicide composition of the present invention is used in the form of a wettable powder, the above-mentioned triazine derivative and quinoline carboxylic acid herbicide are usually used as active ingredients in an amount of 10 to 55% by weight and 4% by weight as a solid carrier.
A composition may be prepared by mixing 0 to 88% by weight of the surfactant and 2 to 5% by weight of the surfactant, and then used. Also,
When used in the form of emulsions and flowables, the active ingredients are usually the triazine derivatives mentioned above, 5 to 50% by weight of quinoline carboxylic acid herbicides, and 35 to 90% by weight of solvents.
and surfactants and other adjuvants 5-15% by weight
It may be prepared by blending them in the following proportions.

On the other hand, when used in the form of a powder, it is usually prepared by blending the above-mentioned triazine derivative as an active ingredient, 1 to 15% by weight of the quinoline carboxylic acid herbicide, and 85 to 99% by weight of the solid carrier.

Furthermore, when used in the form of granules, the above-mentioned triazine derivatives as active ingredients, 0.1 to 15% by weight of a quinoline carboxylic acid herbicide, 80 to 97.9% by weight of a solid carrier, and 2 to 5% by weight of a surfactant. % ratio. Here, fine mineral powder is used as the solid carrier, and examples of the fine mineral powder include oxides such as diatomaceous earth and slaked lime, phosphates such as apatite, sulfates such as ceracola, talc, and pyrochloride. Ferrite clay, kaolin, bentonite, acid clay, white carbon, quartz powder,
Examples include silicates such as silica powder.

In addition, liquid carriers include paraffinic or naphthenic hydrocarbons such as kerosene, mineral oil, and spindle oil, aromatic hydrocarbons such as benzene, toluene, and xylene, and chlorinated hydrocarbons such as 0-chlorotoluene, trichloromethane, and trichloroethylene. , alcohols such as cyclohexanol, amyl alcohol and ethylene glycol, alcohol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, ketones such as isophorone, cyclohexanone, cyclohexenyl-cyclohexanone, and butyl cellosolve.

Organic solvents such as ethers such as dimethyl ether and methyl ethyl ether, esters such as isopropyl acetate, benzyl acetate, and methyl phthalate, amides such as dimethylformamide, nitrites such as acetonitrile and propionitrile, sulfoxides such as dimethyl sulfoxide, or mixtures thereof. Or you can give them water.

Furthermore, as a surfactant, anionic type (alkylbenzene sulfonate, alkyl sulfonate, lauric acid amide sulfonate, etc.) is used.

Nonionic type (polyoxyethylene octyl ether, polyethylene glycol laurate, sorbitan alkyl ester, etc.), cationic type (dimethyllaurylbenzylammonium chloride, laurylamine, stearyltrimethylammonium chloride, etc.), or zwitterionic type (amino acids, betaine, etc.) You can also use

In addition, sodium alginate is added to the herbicide composition of the present invention for the purpose of improving the properties of the preparation and increasing the herbicidal effect.

A polymer compound such as carboxymethylcellulose, carboxyvinyl polymer, gum arabic, hydroxypropylmethylcellulose, or an adjuvant can also be used in combination.

The herbicide composition of the present invention can be applied to field crops such as corn, sorghum, wheat, barley, and oats by soil or foliage treatment before or after the germination of weeds, allowing it to be highly selective and free from phytotoxicity. It exhibits excellent effects as a herbicide. Furthermore, it has a high herbicidal effect on not only annual weeds but also perennial weeds, and is extremely useful as a highly selective herbicide with no chemical damage to paddy rice or lawns.

Furthermore, the herbicide composition of the present invention can also be used to treat weeds in orchards or non-agricultural lands (industrial areas, railway sites, roadsides, riverside sites, fallow land), etc. by applying soil treatment or foliage treatment. Demonstrates pest control effect.

The herbicide composition of the present invention has an active ingredient of 0 per 1O are.
．． About 1 to 10,000g, preferably 1 to 1,000g
Apply g. In addition, when spraying on plant stems and leaves, 1 to 1
Approximately 00.00 oppm, preferably 10 to 10.0
Apply diluted to 00 ppm.

In addition, the herbicidal composition of the present invention can also be used in combination with other herbicidal components. Examples of herbicidal ingredients that can be used here include diphenyl ether-based and triazine-based herbicides, which are conventionally commercially available herbicides.

Phenoxyacetic acid type, carbamate type, thiol carbamate type, acid anilide type, pyrazole type.

Phosphoric acid type, sulfonylurea type, imidazolinone type, dinitroaniline type, bromoxynil, ioxynil,
Examples include oxacycin.

Furthermore, the herbicidal composition of the present invention can be used in combination with an insecticide, monocide, plant growth regulator, fertilizer, etc., if necessary.

〔Example〕

Next, the present invention will be explained by examples.

First, the formulation method will be specifically explained using formulation examples. In addition, "part" in the following manufacturing side means weight%. The compounds shown in Table 1 were used as triazine derivatives (compound A), and the compounds shown in Table 2 were used as quinoline carboxylic acid herbicides (compound B).

Table 1 / Table 1 (Continued) Table 1 (Continued) Table 2 Formulation Example 1 Wettable powder Compound A - 15 parts Compound B - 115 parts Diatomaceous +/- 62 parts White carbon 15 parts Sodium alkylbenzenesulfonate 2 parts Lignin At least 1 part of sodium sulfonate was mixed and pulverized uniformly to obtain 100 parts of a wettable powder.

Formulation Example 2 Emulsion Compound A - 210 parts Compound B - 230 parts Xylene 20 parts Dimethylformamide At least 20 parts were uniformly dissolved and mixed to obtain 100 parts of an emulsion.

Formulation Example 3 Powder Compound A-3 Compound B-2 0.6 parts of diatomaceous earth 1.4 parts 20 parts Talc 78 parts or more were mixed and uniformly mixed and pulverized to obtain 100 parts of a powder.

Formulation Example 4 Granules Compound A - 51 parts Compound B - 13 parts Bentonite 30 parts Talc 63 parts Sodium ligninsulfonate 3 parts or more were mixed well, mixed and pulverized uniformly, water was added and kneaded well, and then granulated and dried. 100 parts of granules were obtained.

Formulation Example 5 70 Apples Compound A - 710 parts Compound B - 215 parts Methyl cellulose 0.3 parts Colloidal silica 1.5 parts Sodium ligninsulfonate 1 part Water 70.2 parts or more were thoroughly mixed and dispersed to form a slurry mixture. Wet grinding yielded 100 parts of a stable flowable agent.

Formulation Example 6 97 parts of clay (trade name Nidikrite, manufactured by Zeeklite Industries) as a wettable powder carrier, 1.5 parts of alkylaryl sulfonate (trade name: Neoperex, manufactured by Kao Atlas ■) as a surfactant, and Nonionic and anionic surfactants (product name: Solpol 800A, Toho Chemical Industry)
A carrier for wettable powders was obtained by uniformly pulverizing and mixing 1.5 parts of the following products.

90 parts of this wettable powder carrier and 10 parts of the triazine derivatives (compounds A-1 to A-7) shown in Table 1, or the quinoline carboxylic acid herbicides (compounds B-1 or B-7) shown in Table 2. -2) 10 parts were uniformly ground and mixed to obtain a wettable powder.

Furthermore, the carrier for a wettable powder containing the triazine derivative obtained above and the carrier for a wettable powder containing a quinoline carboxylic acid herbicide are mixed in a predetermined amount (active ingredient ratio), and the mixture is uniformly mixed and ground. A hydrating agent was obtained.

Example 1 Flooded soil treatment test Paddy soil was filled in a 1/2000 are pot with rice field soil, and on the surface layer, seeds of Japanese wild grass, Japanese cypress, broad-leaved weeds (Kikashigusa, Japanese cypress), and Japanese firefly were evenly sown, and in addition, 1000 square meters of Paddy field soil was sown on the surface layer. Tubers were transplanted, and paddy rice at the two-leaf stage was transplanted.

Thereafter, when the weeds germinated, a predetermined amount of the diluted herbicide obtained in Production Example 6 was uniformly dropped onto the water surface to treat the weeds, and then the pots were left in a greenhouse and watered at appropriate times.

Table 3 shows the results of investigating the herbicidal effect and rice damage after 20 days of chemical treatment. In addition, the drug amount was shown as the amount of active ingredient per 10 ares. In addition, paddy rice damage and herbicidal effects were measured using the air-dried type and expressed as follows.

Rice damage (compared to untreated plot) 100% 95-99% 90-94% 80-89% 60-79% 50-59% Herbicidal effect (compared to untreated plot) 100% 61-99% 21-60% 11-20% 1-10% 0% / Example 2 Growing season treatment test In a 1/2000 are Wagner pot filled with upland soil, weed seeds of staghorn grass, violet, and crop seeds of wheat and barley were sown and covered with soil. After that, the weeds were grown in a greenhouse, and at the 1.5 to 2.5 leaf stage of these weeds and the 3 leaf stage of the crop, a predetermined amount of the herbicide obtained in Formulation Example 6 was suspended in water, and 1001/10 are. A considerable amount of liquid was sprayed uniformly onto the stems and leaves. After that, it is grown in a greenhouse and after treatment 2
On day 0, crop damage and herbicidal effects were evaluated according to the following criteria. The results are shown in Table 4.

(Judgment criteria) Degree of herbicidal effect Herbicidal effect (weed killing rate) Less than % (almost no effect) 5-20% 20-40% 40-70% 70-80% 0% or more (almost completely dead) ) However, the above-mentioned weed killing rate was determined by measuring the weight of above-ground plants in the chemical-damaged area and the weight of above-ground plants in the non-treated area using the following formula.

Degree of phytotoxicity 0... No phytotoxicity to crops was observed 1...
...Hardly any chemical damage to crops was observed2...
...Some chemical damage to crops is observed 3...
- Phytotoxicity to crops is observed 4... Phytotoxicity to crops is noticeably observed 5... Most of the crops wither,\2: Some excerpts from the results shown in Table 4. , triazine derivatives and quinolinecarphonic acid herbicides (
The synergistic effect of compound B-2) was investigated on Yaemugura and Violet.

[Source: Limpel, L, E,, P, H, 5chu
ldt and R. Lamont.

Proc, NEWCC, 16, 48-53 (196
2)) Here, if the actual value (herbicidal rate) of the herbicide obtained by mixing the triazine derivative and the quinolinecarphonic acid herbicide (compound B-2) is larger than QE, it indicates that there is a synergistic effect on the herbicidal activity. This means that it has been expressed. This result is the fifth
Shown in the table.

Example 3 Field test (soil treatment test) Two test plots were made, each plot having an area of two plots.

Weed seeds of poppy and barley and crop seeds of wheat and barley were sown at the same time.

Thereafter, before germination of wheat, barley and weeds, a predetermined amount of the diluted herbicide obtained in Formulation Example 6 was added to 2047/1.
A liquid volume equivalent to 0 are was uniformly sprayed on the soil surface. This test was conducted in triplicate.

After 60 days of spraying, the remaining weeds were cut off from the ground, their fresh weight was measured, and the average weeding rate for the three plots was calculated using the following formula.

In addition, for wheat and barley, the fresh weight of above-ground parts was measured in the same manner as for weeds, and the degree of chemical damage (suppression rate) was determined. 6th result
Shown in the table.

Example 4 Field test (growth season treatment test) Two test plots were made in the area of one plot, and the test plots were planted with violets, chickweed, violets,
Chamomile, flowering plant.

Weed seeds of poppy and barley and crop seeds of wheat and barley were sown at the same time.

After that, weeds reach 2-3 leaf stage and wheat and barley reach 3-leaf stage.
When the leaves reached the leaf stage, a predetermined amount of the herbicide diluted solution obtained in Production Example 6 was uniformly sprayed on the stems and leaves in an amount equivalent to 201/1o are. This test was conducted in triplicate.

Thirty days after the chemical spraying, the herbicidal rate and the degree of chemical damage were determined using the same method as in Example 3. The results are shown in Table 7.

〔Effect of the invention〕

The herbicidal composition of the present invention exhibits a high herbicidal effect at a low dosage due to the synergistic effect of the triazine derivative as its active ingredient and the quinoline carboxylic acid herbicide, and has a wide herbicidal spectrum. In addition, when used as a herbicide for upland fields, the range of suitable chemical treatment is wider than that of existing herbicides for upland fields, and for weeds that are difficult to control, it is also possible to treat weeds during the weed growth period before or during soil treatment. It also shows high activity in foliar and foliage treatments, and does not cause any chemical damage to crops. In particular, the effect is extremely high when applied to soil or foliage treatments in fields of gramineous crops. Furthermore, the herbicide of the present invention has greater efficacy against weeds that are difficult to control than existing herbicides for rice paddy, and has less phytotoxicity.

Claims (1)

[Claims] General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, A is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, Z represents an oxygen atom or a sulfur atom.) or ▲
There are mathematical formulas, chemical formulas, tables, etc.▼ (However, X^2 represents a methyl group or a fluorine atom,
n represents an integer of 0 to 2. ), R^1 represents a hydrogen atom or a methyl group, and X^1 represents a fluorine atom or a chlorine atom. ] There are triazine derivatives represented by the general formula ▲ mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^2 represents a chlorine atom or a methyl group. A herbicide composition containing a quinoline carboxylic acid herbicide represented by the following as an active ingredient.