JPH07316138A - Pyrazolone derivative and herbicide containing the same as active ingredient - Google Patents

Abstract

PURPOSE:To obtain the pyrazolone derivative having an excellent herbicidal effect and useful as a herbicide exhibiting selectivity between crops and weeds. CONSTITUTION:A compound of formula I (R<1> is H, 1-3C alkyl; R<2> is 1-3C alkyl, 1-3C haloalkyl; R<3>, R<4> are H, methyl; X<1>-X<5> are H, halogen, 1-6C alkyl, 1-6C alkoxy, etc.). The compound of formula I is obtained by reacting a pyrazolone compound with an acetal derivative of formula III and subsequently reacting the reaction product with an amine derivative of formula IV. The compound of formula I is effective for various weeds belonging to the families Persicaria, Portulacaceae, Chenopodiaceae, Amaranthaceae, Cruciferae, Leguminosae, Gramineae, etc., and does not exhibit chemical injuries for main crops such as corn, wheat, barley, rice, sorghum, soybean, cotton, beet, peanut and sunflower, and for garden crops such as flowering plants and vegetables.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a pyrazolone derivative and a herbicide containing the same as an active ingredient.

The present inventors have conducted extensive studies to find an excellent herbicide, and as a result, found that a pyrazolone derivative represented by the following general formula 2 has an excellent herbicidal effect, and arrived at the present invention.

That is, the present invention has the general formula

[Chemical 2] [In the formula, R ¹ represents a hydrogen atom or a C ₁ -C ₃ alkyl group (for example, a methyl group, an ethyl group, an isopropyl group, etc.), and R ² is a C ₁ -C ₃ alkyl group (for example, a methyl group, an ethyl group). Group, isopropyl group, etc.) or a C ₁ -C ₃ haloalkyl group (eg, trifluoromethyl group, trichloromethyl group, pentafluoroethyl group, etc.),
R ³ and R ⁴ are the same or different and each represents a hydrogen atom or a methyl group, and X ¹ , X ² , X ³ , X ⁴ and X ⁵
Are the same or different and are hydrogen atom, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), C ₁ to
C ₆ alkyl group (eg, methyl group, ethyl group, isopropyl group, etc.), C ₁ -C ₆ haloalkyl group (eg, trifluoromethyl group, etc.), C ₁ -C ₆ alkoxy group (eg, methoxy group, ethoxy group) Etc.) or a C ₁ -C ₆ haloalkoxy group (eg, trifluoromethoxy group, pentafluoroethoxy group, etc.). ] The pyrazolone derivative shown by these and the herbicide characterized by containing it as an active ingredient are provided. The compounds of the present invention have geometrical isomers (E, Z) derived from a carbon-carbon double bond, and the present invention includes these isomers and mixtures thereof.

Next, the method for producing the compound of the present invention will be described in detail. The compound of the present invention has, for example, a compound represented by the general formula:

[Chemical 3] [In the formula, R ² has the same meaning as described above. ] The pyrazolone compound represented by

[Chemical 4] [In the formula, R ¹ represents the same meaning as described above. ] The acetal derivative represented by

[Chemical 5] [In the formula, X ¹ , X ² , X ³ , X ⁴ , X ⁵ , R ³ and R
⁵ has the same meaning as above. ] It can manufacture by reacting with the amine derivative shown by these.

This reaction is usually carried out without solvent or in a solvent, the reaction temperature range is usually 0 to 200 ° C., and the reaction time range is usually 1 to 50 hours. The amount of the reagent is usually 1 to 10 mol of the acetal derivative of the general formula 4 relative to 1 mol of the pyrazolone compound of the general formula 3, and the amine derivative of the general formula 5 is usually 1 to 1 mol. It is a ratio of 10 mol. Examples of the solvent used include hexane, heptane, ligroin,
Aliphatic hydrocarbons such as petroleum ether, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as chloroform, carbon tetrachloride, dichloroethane, chlorobenzene and dichlorobenzene, diethyl ether, diisopropyl ether, dioxane. , Ethers such as tetrahydrofuran, diethylene glycol dimethyl ether, alcohols such as methanol, ethanol, isopropanol, t-butanol, octanol, cyclohexanol, methyl cellosolve, diethylene glycol and glycerin, esters such as ethyl formate, ethyl acetate, butyl acetate and diethyl carbonate. Kind, nitroethane,
Nitrides such as nitrobenzene, nitriles such as acetonitrile and isobutyronitrile, tertiary amines such as pyridine, triethylamine, N, N-diethylaniline, tributylamine and N-methylmorpholine, formamide, N, N-dimethylformamide. Acid amides such as acetamide, sulfur compounds such as dimethyl sulfoxide and sulfolane, or a mixture thereof. The reaction solution after completion of the reaction is subjected to usual post-treatments such as extraction with an organic solvent and concentration, and if necessary, further purified by a procedure such as chromatography, distillation, recrystallization, etc. to obtain the desired compound of the present invention. be able to.

Next, Table 1 shows examples of the compounds of the present invention.

[Table 1]

The pyrazolone compound represented by the general formula (3), which is a starting material compound for producing the compound of the present invention, is represented by, for example, the general formula (6).

[Chemical 6] [In the formula, R ² has the same meaning as described above. ] It can manufacture by making the (beta) -keto carboxylic acid ester derivative shown by these react with methylhydrazine. This reaction is usually carried out without solvent or in a solvent, the reaction temperature range is usually 0 to 200 ° C., the reaction time range is usually 1 to 50 hours, and the amount of reagents to be used in the reaction is Is
The amount of methylhydrazine is usually 1 to 10 mol per 1 mol of the β-ketocarboxylic acid ester derivative represented by the general formula (6). As the solvent used, for example, hexane, heptane, ligroin, aliphatic hydrocarbons such as petroleum ether, aromatic hydrocarbons such as benzene, toluene, xylene, chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, dichlorobenzene, etc. Halogenated hydrocarbons, diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, ethers such as diethylene glycol dimethyl ether, formic acid, acetic acid,
Fatty acids such as oleic acid, alcohols such as methanol, ethanol, isopropanol, t-butanol, octanol, cyclohexanol, methyl cellosolve, diethylene glycol and glycerin, nitro compounds such as nitroethane and nitrobenzene, pyridine, triethylamine, N, N-diethylaniline. , Tributylamine,
Examples thereof include tertiary amines such as N-methylmorpholine, acid amides such as formamide, N, N-dimethylformamide and acetamide, sulfur compounds such as dimethylsulfoxide and sulfolane, and mixtures thereof. After completion of the reaction, the reaction solution is subjected to usual post-treatments such as extraction with an organic solvent and concentration, and if necessary, further purified by a procedure such as chromatography, distillation, recrystallization and the like to give the pyrazolone compound of the general formula (6). Can be obtained.

The compounds of the present invention have excellent herbicidal efficacy,
Some also show excellent selectivity between crops and weeds. That is, the compound of the present invention has herbicidal activity against various weeds which are the following problems in the treatment of foliage in upland fields. Polygonum convolvulus, weed, weed
lygonum lapathifolium), American sandweed (Polygo
num pensylvanicum), Hartade (Polygonum persicari)
a), Rumex crispus, Rumex obtusifolius, Japanese knotweed (Polygonum cusp)
idatum) Portulaca oleracea Portulaca oleracea Stellaria media Stellaria media Stellaria media Weed weeds (Chenopodium album), Hochigi (Kochia scopa)
ria) Amaranthaceae weed Amaranthus retroflexus, stag beetle Amaranthushybridus Brassica weed Wild radish (Raphanus raphanistrum), field bean (Sinapis arvensis), cucumber (Capsella bur)
sa-pastoris Leguminous weeds American hemlock (Sesbania exaltata), Ebisugusa (Cassia obtusifolia), Florida beggerweed (Desmodium tortuosum), White clover (Trifolium re)
pens) Mallow family weed Abutilon theophrasti, Sida spinosa, Violet arvensis, Wild pansy ), Malva morning glory (Ipomoea purpurea), Malva american morning glory (Ip
omoea hederacea var. integriuscula), ground beetle (Ipomoea lacunosa), bindweed (Convolvulu)
s arvensis) Laminium purpureum (Lamium purpureum), Lamium amplexicaure (Lamium amplexicaure) Weeds of Solanaceae (Datura stramonium) (Xanthium pensylvanicum), wild sunflower (Helianthus annuus), dog chamomile (Matricaria per
forata), corn marigold (Chysanthemumsegetu
m), forsythia (Matricaria matricarioides), ragweed (Ambrosia artemisiifolia), and red ragweed (Amb
rosia trifida), Sagebrush (Erigeron canade)
nsis), Wormwood (Artemisia princeps), Solidago altissima (Echinochloa crus-galli), Echinochloa crus-galli, Setaria viridis,
beri), crabgrass (Digitaria sanguinalis), crabgrass (Eleusine indica), Poa annua,
Blackgrass (Alopecurus myosuroides), oats (Avena fatua), Seymour sorghum (Sorghum halepe)
ns), Shatter cane (Sorghum vulgare), Commelina communis, and some of the compounds of the present invention are corn (Zea mays), wheat (Triticum aestivum), barley (Hordeum vulgare), rice (Oryza sativa). ), Sorghum (Sorghum bicolor), soybean (Glycine max), cotton (Go
ssypium spp.), sugar beet (Beta vulgaris), peanuts (Arachis hypogaea), sunflower (Helianthus annuu)
s), rapeseed (Brassica napus), and other horticultural crops such as flowers and vegetables.

Further, the compound of the present invention has herbicidal activity against various weeds which cause the following problems in the flooding treatment of paddy fields. Weeds in grasses Echinochloa oryzicola Lindernia procumbens Weeds in the family Lynnia procumbens Rotora indica, Ammannia
multiflora) Weed weed (Elatine triandra) Weed weed (Monochoria vaginalis) Weed weed (Potamogeton distinctus) Weed weed (Oenan the javanica) Moreover, some of the compounds of the present invention are directly transplanted paddy rice. It does not show any harmful drug damage. Further, the compounds of the present invention are capable of weeding a wide range of weeds that occur in orchards, pastures, lawns or forests or other non-agricultural lands.

When the compound of the present invention is used as an active ingredient of a herbicide, it is usually mixed with a solid carrier, a liquid carrier, a surfactant or other formulation auxiliary agents to prepare an emulsion, a wettable powder, a suspension,
Formulated in granules, wettable granules, etc. These formulations contain the compound of the present invention as an active ingredient in a weight ratio of 0.2 to 80%, preferably 1 to 70%. As a solid carrier, kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, mineral fine powder such as calcite, organic fine powder such as walnut shell powder,
Examples thereof include fine powders of water-soluble organic substances such as urea, fine powders of inorganic salts such as ammonium sulfate, and fine powders of synthetic hydrous silicon oxide, and the liquid carrier is an aromatic such as alkylbenzene such as methylnaphthalene, phenylxylylethane, and xylene. Hydrocarbons, alcohols such as isopropanol, ethylene glycol and 2-ethoxyethanol, esters such as dialkyl phthalate, ketones such as acetone, cyclohexanone and isophorone, mineral oil such as machine oil, soybean oil and cottonseed oil Vegetable oil, dimethyl sulfoxide, N, N-dimethylformamide, acetonitrile, N-methylpyrrolidone and the like can be mentioned. Surfactants used for emulsification, dispersion, wet spreading, etc. include alkyl sulfate ester salts, alkyl sulfonates, alkylaryl sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkylaryl ether phosphate ester salts, etc. Anionic surfactant, polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene polyoxypropylene block copolymer, sorbitan fatty acid ester,
Examples thereof include nonionic surfactants such as polyoxyethylene sorbitan fatty acid ester. Other auxiliaries for formulation include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC (carboxymethyl cellulose), PAP (isopropyl acid phosphate) and the like. The compound of the present invention is usually formulated and subjected to foliar treatment or flooding treatment before or after emergence of weeds. The foliage treatment includes not only treatment from above the plant body but also local treatment such as treatment of only weeds so as not to adhere to crops. Also, by mixing with other herbicides,
Increased herbicidal efficacy may be observed. Furthermore, it can be used by mixing with insecticides, acaricides, nematicides, fungicides, plant growth regulators, fertilizers and the like.

When the compound of the present invention is used as an active ingredient of a herbicide, the amount to be treated varies depending on weather conditions, formulation form, treatment time, treatment method, target crops, target weeds, etc., but usually 50 g / ha or more. It is 10000 g, preferably 100 to 8000 g. For emulsions, wettable powders, suspensions, granule wettable powders, etc., the prescribed amount is usually 1 per hectare.
Dilute with 0 to 1000 liters of water (adding auxiliary agent such as spreading agent if necessary), and treat granules, certain suspending agents, etc. without any dilution.
As the auxiliary agent, in addition to the above-mentioned surfactant, polyoxyethylene resin acid (ester), lignin sulfonate, abietic acid salt, dinaphthylmethane disulfonate, crop oil concentrate (crop oil concentrate),
Vegetable oils such as soybean oil, corn oil, cottonseed oil, sunflower oil and the like can be mentioned. Further, the compound of the present invention can be used as an active ingredient of a harvesting aid such as a cotton defoliant / desiccant and a potato (Solanum tuberosum) desiccant. In that case, the compound of the present invention is usually formulated as in the case of being used as an active ingredient of a herbicide, and foliar treatment is performed alone or in combination with other harvesting aids before harvest of a crop.

[0011]

The present invention will be described in more detail below with reference to production examples, formulation examples and test examples, but the present invention is not limited to these examples. First, production examples of the compound of the present invention will be shown. Production Example 1 1.5 g of 1,3-dimethyl-2-pyrazolin-5-one and 1.6 g of 1,1-dimethoxytrimethylamine were added to 30 ml of tetrahydrofuran, and the mixture was stirred at room temperature for 24 hours. In this solution, 3,4-dichlorobenzylamine
2.6 g was added, and the mixture was stirred at room temperature for 24 hours. The solvent of this reaction solution was distilled off under reduced pressure, and the residue was subjected to column chromatography to obtain the target compound 1 (1.3 g).

Next, some of the compounds of the present invention are shown in Table 2 together with the compound numbers and the physical properties.

[Table 2]

Next, formulation examples are shown. The compounds of the present invention are shown by the compound numbers in Table 2. Parts are parts by weight. Formulation Example 1 50 parts of each of the compounds (1) to (12) of the present invention, 3 parts of calcium ligninsulfonate, 2 parts of sodium lauryl sulfate and 45 parts of synthetic hydrous silicon oxide are well pulverized and mixed to obtain each wettable powder. . Formulation Example 2 10 parts of each of the compounds (1) to (12) of the present invention, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzene sulfonate, 35 parts of xylene and 35 parts of cyclohexanone are mixed well and each emulsion is prepared. To get Formulation Example 3 2 parts of each of the compounds (1) to (12) of the present invention, 2 parts of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 64 parts of kaolin clay are well pulverized and mixed, and water is added. After thoroughly kneading, granulate and dry to obtain each granule. Formulation Example 4 25 parts of each of the compounds (1) to (12) of the present invention, 50 parts of a 10% aqueous solution of polyvinyl alcohol, and 25 parts of water are mixed, and wet-milled until the average particle size becomes 5 μm or less. Obtain a suspension.

Next, it is shown in Test Examples that the compound of the present invention is useful as an active ingredient of a herbicide. The compounds of the present invention are shown by the compound numbers in Table 2. For the evaluation of herbicidal efficacy and phytotoxicity, "0" was used when the emergence or growth of the test plants (weeds and crops) at the time of the survey had no or almost no difference compared to that of the untreated plants. The one completely dying or the germination or the growth being completely suppressed is defined as "5", and is classified into 6 stages of 0 to 5, 0, 1, 2,
Shown as 3, 4, and 5. Evaluation of herbicidal efficacy "4" and "5"
Means an excellent herbicidal effect, and a rating of "3" or less means an insufficient herbicidal effect. Evaluation of phytotoxicity “0” and “1” means that phytotoxicity is not a practical problem, and evaluation of “2”
The above means that no drug damage is allowed. Test Example 1 Field and foliage treatment test Soil was packed in a cylindrical plastic pot having a diameter of 10 cm and a depth of 10 cm, and the morning glory and wild radish were sowed and grown in a greenhouse for 7 days. Then, Formulation Example 2
The test compound was made into an emulsion in accordance with the procedure of 1. and a predetermined amount thereof was diluted with water containing 1000 liters of spreading agent per hectare, and sprayed uniformly from above the plant body over the entire foliage with a sprayer. After the treatment, the plants were grown in a greenhouse for 19 days and the herbicidal efficacy was investigated. The results are shown in Table 3.

[Table 3]

Test Example 2 Paddy Water Submersion Treatment Test Soil was packed in a cylindrical plastic pot having a diameter of 9 cm and a depth of 11 cm, and seeds were sown. After flooding to make it into a paddy field, 2-leaf stage rice was transplanted and grown in a greenhouse. 5
After a day, the test compound was made into an emulsion according to Formulation Example 2, a predetermined amount of the compound was diluted with water, and 50 liters of the diluted solution per are were treated on the water surface. After the treatment, the plants were grown in a greenhouse for 19 days, and herbicidal efficacy and phytotoxicity were investigated. The results are shown in Table 4.

[Table 4]

Test Example 3 Field and foliage treatment test Soil was filled in a plastic pot having an area of 25 × 18 cm ² and a depth of 7 cm, soybean, corn, cotton and dog physalis were sown and grown for 16 days. Then, the test compound was made into an emulsion according to Formulation Example 2, a predetermined amount thereof was diluted with water equivalent to 1000 liters per hectare, and the entire foliage portion was treated uniformly from above the plant body with a sprayer. At this time, the growth conditions of weeds and crops differ depending on the grass species, but 0.5 to 4
At the leaf stage, the plant height was 5 to 30 cm. The herbicidal efficacy and phytotoxicity were investigated 18 days after the treatment. The results are shown in Table 5.
The test was conducted in a greenhouse throughout the entire period.

[Table 5]

[0017]

The compound of the present invention exhibits excellent herbicidal activity.

Claims (2)

[Claims] 1. A general formula: ## STR1 ##[In the formula, R¹Is a hydrogen atom or C₁~ C₃Alkyl group
Represent, R²Is C₁~ C ₃Alkyl group or C₁~ C₃
Represents a haloalkyl group, R³And R^FourAre the same or
Differently, it represents a hydrogen atom or a methyl group, and X¹, X
², X³, X^FourAnd X^FiveAre the same or different, hydrogen
Atom, halogen atom, C₁~ C₆Alkyl group, C₁~ C
₆Haloalkyl group, C₁~ C₆Alkoxy group or C₁
~ C₆Represents a haloalkoxy group. ] Pirazo
Ron derivative. 2. A herbicide containing the pyrazolone derivative according to claim 1 as an active ingredient.