JPH0253775A - Pyrazole carboxamide derivative and herbicide - Google Patents

Abstract

NEW MATERIAL:A compound of formula I [R is H or 1-6C alkyl which may have a substituent (e.g., 1-4C alkoxy or halogen); R<1> is H, halogen, NO2 or 1-4C alkyl which may have a substituent (e.g., 1-4C alkoxy, 1-4C alkylthio or halogen); X<1>-X<3> are H, 1-6C alkoxy or 1-6C holoalkoxy; X<1> and X<2> are further halogen, 1-6C alkyl, 1-6C holoalkyl, phenoxy, aralkyloxy, alkoxyalkoxy, 2-6C alkenyloxy, etc.; W is O or S]. EXAMPLE:A compound of formula II. USE:A herbicide having high herbicidal effects at low doses and excellent selectivity for certain kinds of crops, especially leguminous plants and gramineous plants and further reduced in chemical injuries against crops, in the danger of environmental pollution caused by the application of large amounts and in affections caused by the residue of the herbicide against other crops. PREPARATION:A compound of formula III is reacted with a compound of formula IV to provide the compound of formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to novel pyrazole carboxamide derivatives and herbicides containing one or more of these derivatives as active ingredients.

(b) Conventional technology It has generally been pointed out that the economic cost of using herbicides is influenced by the amount of active ingredient treated per unit area. There is a desire for the emergence of new herbicides that require lower dosages.

On the other hand, conventional herbicides can have an adverse effect on crops when used, and research has continued for many years into compounds that have high herbicidal effects at low doses and higher selectivity between crops and weeds. It's here.

For example, JP-A-63-48269, JP-A-62-
Publication No. 249975, Japanese Patent Application Publication No. 1988-10066,
JP-A-61-280480, JP-A-61-106
Although it is known that pyrazole carboxamide derivatives are used as active ingredients of fungicides in Japanese Patent Application Laid-open No. 559, Japanese Patent Application Laid-open No. 60-34949, and Japanese Patent Application Laid-Open No. 52-87168, there is no information regarding herbicidal activity. Not mentioned.

(C) Mode of the Invention As a result of many years of research, the present inventors have found that the pyrazole carboxamide derivative of the present invention has a significantly higher herbicidal effect than conventional herbicides, and that many of the pyrazole carboxamide derivatives of the present invention , has excellent selectivity and is practically useful for crops consisting of legumes, especially leguminous plants, grasses, such as soybeans, transplanted paddy rice, etc., and is also useful for crops such as important weeds such as wild grass, blackberry, and cyperus. The present invention was completed based on the discovery that the present invention has excellent activity in the following: , Japanese dogwood, Japanese leafminer, Japanese firefly, Japanese firefly, Japanese cypress, Japanese cypress, and Japanese apricot.

In other words, the pyrazole carboxamide derivative of the present invention can significantly reduce the amount of active ingredient applied per unit area compared to conventionally known compounds, and has extremely minimal phytotoxicity to crops compared to conventional herbicides, making it economically viable. The effect is extremely large.

Furthermore, the pyrazole carboxamide derivative of the present invention can significantly reduce the risk of environmental pollution caused by applying large amounts of pesticides, and can be said to be an epoch-making herbicide that has little adverse effect on other crops due to residual soil.

The present invention is based on the general formula (1) [wherein R is a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms (this substituent includes 1 to 6 carbon atoms)]
~4 alkoxy group and halogen atom. ) is shown.

R1 is a hydrogen atom, a halogen atom, a nitro group, or an optionally substituted alkyl group having 1 to 6 carbon atoms (this substituent includes an alkoxy group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms,
represents an alkylthio group and a halogen atom. ) is shown.

XI, X! is hydrogen atom, halogen atom, carbon number 1-6
Alkyl group having 1 to 6 carbon atoms, haloalkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, haloalkoxy group having 1 to 6 carbon atoms, phenoxy group, aralkyloxy group, alkoxyalkoxy group, alkenyl having 2 to 6 carbon atoms Oxy group, alkynyloxy group having 2 to 6 carbon atoms, alkylthio group having 1 to 6 carbon atoms, haloalkylthio group having 1 to 6 carbon atoms, alkylsulfonyl group having 1 to 6 carbon atoms, haloalkylsulfonyl having 1 to 6 carbon atoms group, an alkoxycarbonyl group having 1 to 6 carbon atoms, an alkylcarbonyl group having 1 to 6 carbon atoms, a nitro group, a cyano group, or an alkylamino group having 1 to 6 carbon atoms.

X3 represents a hydrogen atom, an alkoxy group having 1 to 6 carbon atoms, or a haloalkoxy group having 1 to 6 carbon atoms.

W represents an oxygen atom or a sulfur atom.

In addition, x' and x'' together form a 5-membered ring or a 6-membered ring containing 1 to 2 oxygen atoms.
You can do it. ] -Z: This relates to a pyrazole carboxamide derivative represented by h and a herbicide containing one or more of the derivatives as an active ingredient.

The pyrazole carboxamide derivative of the present invention is a novel compound that has not been described in any literature, and has excellent physiological activity as a herbicide.

The pyrazole carboxamide derivative represented by the general formula CI) of the present invention can be obtained by reacting a carboxylic acid halide represented by the general formula (■) W with an aniline derivative represented by the general formula (III) HX+ (2, Therefore, it can be manufactured.

In this case, a suitable solvent such as benzene, toluene,
Hydrocarbons such as xylene, halogenated hydrocarbons such as chlorobenzene/zene, methylene chloride, chloroborum, carbon tetrachloride, ethers such as diisopropyl ether, tetrahydrofuran, dioxane, ketones such as acetone, methyl ethyl ketone, ethyl acetate, etc. esters, nitriles such as acetonitrile, dimethyl sulfoxide, dimethyl formamide, water, etc., or without a solvent, usually 0.4 to 1.5 equivalents, preferably 0.5 to 1.1 equivalents. A carboxylic acid halide represented by formula (II) is reacted.

In addition, carboxylic acid halide represented by general formula (II),
The general formula (II
It is also possible to add and react the aniline derivative represented by I).

The reaction can be carried out at any temperature from the freezing point to the boiling point of the solvent, preferably from 0°C to the boiling point of the solvent, and can be heated or cooled as necessary.

Examples of the carboxylic acid halide represented by general formula (II) include carboxylic acid fluoride, carboxylic acid chloride, and carboxylic acid bromide.

Furthermore, in the above reaction, 1 um of sodium hydroxide as a deoxidizing agent,
Potassium hydroxide, triethylamine, N-methylmorpholine, pyridine, etc. can be used.

The amount of these deoxidizing agents used is usually in the range of catalytic amount to 2 equivalents, but preferably in the range of 0.95 to 1.1 equivalents.

The pyrazole carboxamide derivative of the present invention obtained by the above production method can also be purified by recrystallization or column chromatography, if necessary.

The present invention will be explained in more detail below using synthesis examples, formulation examples, and test examples, but the present invention is not limited thereto.

Kin Ikan 1 Synthesis of 3-F.Lifluoro-1-methylpyrazole-4carboxylic acid 111-) Lifluoropenkune-2,4-dione 75g
(0,49 mol) of ethanol 300 mh capacity / night 15
22.・1g of methylhydrazine, keeping it below C.
0.48 mol) was slowly added dropwise.

After stirring for 1 hour, the solvent was distilled off, water was added, and the mixture was extracted with ether. The ether was distilled off under reduced pressure to give 15-dimethyl-
57 g of crude product of 3-trifluoromethylpyrazole (
A yield of 72% was obtained.

After adding 1800 ml of water to this, 65.4 g of potassium permanganate was added and the mixture was heated under reflux for 2 hours.

Furthermore, 65.4 g of potassium permanganate was added and heated under reflux for 2 hours.

After cooling the reaction solution, solids were removed by filtration.

The resulting aqueous layer was extracted with benzene, acidified with hydrochloric acid, extracted with chloroform, the organic layer was separated, and the solvent was distilled off under reduced pressure to give 3-trifluoro-1-methylpyrazole-
46 g (yield 65%) of 4-carboxylic acid was obtained.

Physical properties Melting point, 135.0-136.0°C PMR (δ(CDCl 3+ DMSOdb) 4.18
(s, 311), 6.97 (s, 18), 13
．． 00 (bs, IH) Synthesizer 1 3-trifluoromethyl-1-ethylpyrazole-5-
Synthesis of carboxylic acid 31 g (0.2 mol) of trifluoroacetylacetone and 80 ml of ethanol 1. was added and cooled in a water bath.

After 10.1 g of hydrazine monohydrate was added dropwise thereto, the mixture was heated under reflux for 2 hours.

After evaporating the solvent under reduced pressure, chloroform was added to the residue, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain 3-
Trifluoromethyl-5-methyl IH pyrazole and 5-
27 g of a mixture of trifluoromethyl-3-methyl-IH pyrazole were obtained.

Next, n-hexane washed sodium hydride 1,85
g was suspended in 50 ml of dimethylformamide and cooled in a water bath.

To this suspension was added 5.25 g (0,03
5 mol) dimethylformamide solution 10ml! was dripped. After stirring at room temperature for 1 hour, 6.2 g of ethyl iodide was added while cooling in a water bath, and the reaction solution, which was stirred at room temperature for 2 days, was neutralized with acetic acid, extracted with benzene, washed with water, and dried over anhydrous sodium sulfate.

Next, after passing through the mouth anhydrous sodium sulfate, the solvent was distilled off, and 3-
5.24 g of a mixture of trifluoromethyl-5-methyl-1-ethylpyrazole and 3-methyl-5-trifluoromethyl-1-ethylpyrazole was obtained.

3-trifluoromethyl-5-methyl-1-ethylpyrazole and 3-methyl-5-trifluoromethyl-1-ethylpyrazole? 5 g (28 mmol) of R combined %h was added to a solution of 8.9 g of potassium permanganate and 180 ml of water, and 1 lot of 0.1 g of tetrabutylammonium hydrogen sulfate was heated under reflux for 2 hours.

After cooling the reaction solution, it was passed through Celite, and diluted hydrochloric acid was added to the 0 solution to precipitate white crystals. When this crystal is dried, 1.
It was 7g. From PMR, 3-trifluoromethyl-
It was 1-ethylpyrazole-5-carboxylic acid.

Main ingredients: Synthesis of 3-trifluoromethyl-1-trifluoroethylpyrazole-5-carboxylic acid CI1. C.F.

Dissolve 23.6 g (0.15 mol) of trifluoroacetylacetone in 50 ml of ethanol and heat at -30 to 40°C.
It was cooled to

Next, 70% trifluoroethylhydrazine aqueous solution 25
After adding g dropwise, the mixture was stirred at room temperature for 15 minutes and further heated under reflux for 1 hour.

After distilling off the solvent under reduced pressure, it was distilled under reduced pressure to obtain a mixture of 3-trifluoromethyl-5-methyl-1-trifluoroethylpyrazole and 3-methyl-5-trifluoromethyl-1-trifluoroethylpyrazole (6: 4) 23.4
g (boiling point 72-78°C/22mmHg) was obtained.

16.0 g of this mixture was mixed with 12 g of potassium permanganate.
, 4 g and 150 rtdl of water, added to a solution of 80-9
After heating at 0°C for 1 hour, add potassium permanganate 12
．． 4 g was added and heated for 4 hours.

After the reaction solution was cooled, it was passed through Celite, and when hydrochloric acid was added to the 0 solution to make it weakly acidic, white crystals were precipitated.

The crystals were dried to obtain 4.2 g of 3-trifluoromethyl-1-trifluoroethylpyrazole-5-carboxylic acid.

Synthesis of 3-trifluoromethyl-4-chloro-1-methylpyrazole-5-carboxylic acid C1]3 25 g (0.16 mol) of trifluoroacetylacetone
was dissolved in 100 ml of ethanol, and 7.4 g of methylhydrazine was added dropwise while keeping the temperature below 15°C.
Stir for hours.

After the reaction is completed, the solvent is distilled off under reduced pressure, and further distilled under reduced pressure to obtain 3-
Trifluoromethyl-5-methyl-1 methylpyrazole 18.63g (yield 71%, boiling point 95-96°C/3
1 mmmm 1 liter was obtained.

3 g of this 3-trifluoromethyl-5-methyl-1-methylpyrazol was dissolved in 50 ml of carbon tetrachloride, and 3.65 g of N-chlorophthalic acid imide was added thereto, followed by heating under reflux.

After the reaction was completed, the reaction solution was washed with water, and the solvent was distilled off under reduced pressure to obtain 3.4 g (yield: 94%) of 3-trifluoromethyl-4-chloro-5-methyl-1-methylpyrazole.

This 3-trifluoromethyl-4-chloro-5methyl-
1°Omfl of water and 5g of potassium permanganate were added to 3.4g of 1-methylpyrazole, and the mixture was heated under reflux for 2 hours.

After the reaction was completed, the mixture was passed through Celite, hydrochloric acid was added to the solution to make it weakly acidic, extracted with ethyl acetate, and dried over anhydrous sodium sulfate.

The solvent was distilled off under reduced pressure to obtain 1.5 g of 3-trifluoromethyl 4-chloro-1-methylpyrazole-5-carboxylic acid (
A yield of 38%) was obtained.

Synthesis of 3-trifluoromethyl-1-isopropylpyrazole-5-carboxylic acid 1.85 g of n-hexane-washed sodium hydride was suspended in 50 ml of dimethylformamide and cooled in a water bath.

To this suspension, 5.25 g of the mixture of 3-trifluoromethyl-5-methyl-IH pyrazole and 5-trifluoromethyl-3-methyl-IH pyrazole obtained in Synthesis Example 2 was added.
(0,035 mol) in dimethylformamide solution 10
mfl was added dropwise. After stirring at room temperature for 1 hour, 6.8 g of isopropyl iodide was added while cooling in a water bath, and the mixture was stirred at room temperature for 2 hours.
The mixture was stirred for several days.

The reaction solution was neutralized with acetic acid, extracted with benzene, washed with water, and dried over anhydrous sodium sulfate.

After passing through anhydrous sodium sulfate, the solvent was distilled off, and 5.4 g of a mixture of 3-trifluoromethyl-5-methyl-1-isopropylpyrazole and 3-methyl-5-trifluoromethyl-1-isopropylpyrazole was obtained. Obtained.

This above 3-trifluoromethyl-5-methyl-1-
1.6 g of a mixture of isopropyl pyrazole and 3-methyl-5-trifluoromethyl-1-isopropyl pyrazole
was autooxidized in an autoclave using a cobalt and manganese catalyst to obtain 0.86 g (yield 54%) of 1-isopropyl-3-trifluoromethyl 5-pyrazolecarboxylic acid.

Synthesis of Compound No. 20 of the Invention Compound No. 20 A benzene solution containing 25 g (0,129 mol) of 3-trifluoro-1-methylpyrazole-4-carboxylic acid obtained in Synthesis Example 1 and 30 g of thionyl chloride was heated to reflux.

After confirming that the generation of hydrochloric acid had stopped, the solvent was distilled off under reduced pressure to obtain carboxylic acid chloride in an almost quantitative yield.

2.1 g of this carboxylic acid chloride was added dropwise to a solution of 50 g of methylene chloride containing 1.5 g of 3-isopropoxyaniline and 1.2 g of triethylamine, and the mixture was stirred at room temperature for 2 hours.

Next, the reaction solution was poured into cold water, and after separation, the aqueous layer was extracted with ethyl acetate. After drying the obtained organic layer, the solvent was distilled off under reduced pressure.

The residue was crystallized using a mixed solvent of isopropyl ether/n-hexane, and 2.6 g of the present compound (No. 20) was obtained.
I got it.

Compounds of the present invention obtained by a synthesis method similar to Synthesis Example 6 are shown in Table 1, and spectral data of representative compounds are shown in Table 2.

Furthermore, the compounds of the present invention obtained by the same synthesis method as Synthesis Example 6 are shown in Table 3.

The compound Nα of the present invention in Table 1 is referred to in the following formulation examples and test examples.

When applying the pyrazole carboxamide derivative of the present invention as a herbicide, -i is a suitable carrier, such as a solid carrier such as clay, talc, bentonite, diatomaceous earth, water, alcohols (methanol, ethanol, etc.),
Aromatic hydrocarbons (benzene, toluene, xylene, etc.)
, chlorinated hydrocarbons, ethers, ketones, esters (ethyl acetate, etc.), acid amides (dimethylformamide, etc.).
Emulsifiers, dispersants, suspending agents, penetrating agents, spreading agents, as desired.
By adding stabilizers, etc., liquid formulations, emulsions, wettable powders, powders, granules, etc.
It can be put to practical use in any form such as a flowable agent.

The content of the active ingredient compound in these preparations is not particularly limited, but is generally 0.10 to 90.0.
A weight percent range is desirable.

Further, if necessary, it may be mixed with other herbicides, various insecticides, fungicides, plant growth regulators, synergists, etc. during formulation or spraying.

For example, the Farm Chemicals Handbook (Far
m Chemicals Handbook), No. 74
ed., 1988, etc.

In addition, the pyrazole carboxamide derivative of the present invention can be used in fields,
In addition to agricultural and horticultural areas such as rice fields and orchards, it can also be used to control various weeds in non-agricultural areas such as playgrounds, vacant lots, and railroad tracks. There are differences depending on the species, cultivated crops, etc., but in general, the amount of active ingredients is O.OO5-10k per hectare.
Approx.

Next, examples of formulations of herbicides containing the pyrazole carboxamide derivative of the present invention as an active ingredient will be shown, but the invention is not limited thereto.

In addition, in the following formulation examples, "part" means part by weight.

Sputum-elbow active ingredient 15 to 75 parts, preferably 10 to 50 parts, especially 15 to 40 parts.

Liquid carrier: 95 to 25 parts, preferably 88 to 30 parts,
Particularly preferably 82 to 40 parts.

Surfactant: 1 to 30 parts, preferably 2 to 20 parts.

1-Active ingredient: 1 to 50 parts, preferably 5 to 45 parts, particularly preferably 10 to 40 parts.

Surfactant: 1 to 30 parts, preferably 2 to 25 parts, particularly preferably 3 to 20 parts.

Liquid carrier: 20 to 95 parts, preferably 30 to 93 parts,
Particularly preferably 57 to 85 parts.

Mono 2 J Germany Active ingredient 20.5 to 10 parts.

Particularly preferred is 15 to 40 parts.

Solid carrier: 95.5 to 90 parts.

Suyuuee Fire Force Active ingredient: 15 to 75 parts, preferably 10 to 50 parts.

Water: 94 to 25 parts, preferably 90 to 30 parts.

Surfactant = 1 to 30 parts, preferably 2 to 20 parts.

Active ingredient: 2.5 to 90 parts, preferably 10 to 80 parts, particularly preferably 20 to 75 parts.

Surfactant: 0.5 to 20 parts, preferably 1 to 15 parts,
Particularly preferably 2 to 10 parts.

Liquid carrier: 5 to 90 parts, preferably 7.5 to 88 parts,
Particularly preferably 16 to 56 parts.

grain-”re Active ingredient -0.1 to 30 parts.

Solid carrier: 99.5 to 70 parts.

Solutions and emulsions are prepared by dissolving the active ingredient in a liquid carrier containing a surfactant. Wettable powders are prepared by mixing a surfactant, a solid carrier, and an active ingredient, and then grinding the mixture.

Powders are prepared by mixing the surfactant, solid carrier and active ingredient and, if necessary, further grinding.

Flowable agents are prepared by suspending or dispersing active ingredients in an aqueous solution containing a surfactant. Granules are prepared by mixing the active ingredient and adjuvants.

Part 1 Wettable powder Compound of the present invention No. 20...
・50 parts Sieglite PFP... River...
・43 parts (Kaolin clay: Sieglite Kogyo ■Product name) Tsurupol 5039 ・Old... 5 parts (
Mixture of nonionic surfactant and anionic surfactant: Toho Chemical Industry ■Product name) Cuplex (anti-caking agent) 2 parts (mixture of surfactant and white carbon: Shiono (Gi Seiyaku ■Product name) Mix and grind the above ingredients uniformly to make a wettable powder. 7 for use
For example, dilute the hydrating agent described in 1 10 to 10,000 times to obtain an active ingredient amount of 0.005 kg to 10 kg per hectare.
Spread it so that it becomes g.

A3γ Example D Emulsion Compound of the Invention Nα36 ・・・・・・・・・1
Parts
・Former---70 parts dimethylformamide
... Old... Part 1 Tsurupol 2680 ・
...Old...1 part (mixture of nonionic surfactant and anionic surfactant: Toho Chemical Industry ■trade name) or more is mixed uniformly to form an emulsion. When used, the above emulsion is diluted 10 to 10,000 times and spread at an amount of active ingredient of 0.005 kg to 10 kg per hectare.

Kikinjol Granule Compound of the Invention No. 37 ・・・・・・・・・
・ Part 5 Hentnight ・・・・・・・・・
・・54 copies ・l
1...40 parts calcium ligninsulfonate...
... One or more parts are uniformly mixed and pulverized, a small amount of water is added, the mixture is stirred, and the mixture is granulated using an extrusion type granulator and dried to form granules. When used, the above emulsion is spread at an amount of active ingredient of 0.005 kg to 10 kg per hectare.

Flowable agent Compound of the present invention Nα38...Old...25 parts Tsurupol 3353...Old...10 parts (
Nonionic surfactant: Toho Chemical Co., Ltd. ■Product name) Lunonx 100OC... Old... 0.5 part (Anionic surfactant: Toho Chemical Co., Ltd. ■Product name) 1% xanthan gum aqueous solution...・・・20 parts (natural polymer) Water ・・・・・・
44.5 part Tsurupol 3353, Lunox 100OC
and 1% aqueous xanthan gum solution were uniformly dissolved in water, and then the compound of the present invention N038 was added and stirred well, followed by wet grinding in a sand mill to obtain a flowable agent.

When using, apply the above flowable agent to 10~10°00
The amount of active ingredient when diluted to 0 times is 0.00 per hectare.
Distribute to weigh between 5kg and 10kg.

Next, the usefulness of the compounds of the present invention as herbicides will be specifically explained in the following test examples.

Inana Toni L Weeding effect test by soil treatment 30cm long,
Sterilized diluvial soil was placed in a plastic box measuring 22 cm wide and 6 cm deep, and rice, wild grass, cyperus, dogfish, dog mustard, corn, wheat, soybean,
After sowing cotton and Japanese leafminer and covering the soil to a depth of about 1.5 cm, the amount of the active ingredient was uniformly spread over the soil surface at a predetermined ratio.

The chemical solution used for spraying was the liquid formulation, wettable powder, emulsion or flowable formulation of the formulation example described above, diluted with water and sprayed over the entire surface using a small sprayer. Four weeks after spraying the chemical solution, the herbicidal effect on various weeds was investigated according to the following criteria.

Judgment criteria 5... Weed killing rate 90% or more (almost complete death) 4... Weed killing rate 70-90% 3... Weed killing rate 40-70% 2... Weed killing rate 20-40% ■... Weed killing rate 5-20% 0...Weed killing rate 5% or less (almost ineffective) However, the above weed killing rate is determined by measuring the above-ground grass weight in the chemical-treated area and the above-ground grass weight in the untreated area. It was calculated using the following formula.

In addition, phytotoxic damage to various crops was investigated according to the following criteria. The results are shown in Table 4.

Judgment Criteria 5: The crop is almost completely dead 4: The phytotoxicity of the crop is significant 3: The phytotoxicity of the crop is observed 2: The phytotoxicity of the crop is slightly observed 1: There is almost no phytotoxicity of the crop O, which is rarely observed...Trial no chemical damage to crops is observed ■2) Vertical herbicidal effect test by seedling leaf treatment 3
Sterilized diluvial soil was placed in a plastic box measuring 0 cm, width 22 cm, and depth 6 cm, and the seeds of rice, wild grass, cyperus, japonica, cypress, corn, wheat, soybean, cotton, and beet were sown in spots. The soil was then covered with approximately 1.5 cm of soil. When each plant reached the 2nd to 3rd leaf stage, the active ingredient was uniformly sprayed onto the violet leaves so that the amount of the active ingredient was in a predetermined ratio.

The chemical solution used for spraying was the liquid formulation, wettable powder, emulsion or flowable formulation of the formulation example described above, which was diluted with water and sprayed over the entire surface of the violet leaves of various weeds and crops using a small sprayer.

Four weeks after spraying the chemical solution, the herbicidal effects on various weeds and the chemical damage to various crops were investigated according to the criteria of Test Example-1. The results are shown in Table 5.

Test 1 - Herbicidal effect test under flooded conditions 115,000
After putting alluvial soil in Earl's Hugner pot, water is added and mixed to create a freshwater condition with a water depth of 2CI11. Seeds of Japanese millet, Japanese grass, Kikashigusa, and Firefly were mixedly sown in the above pots, and then rice seedlings at the 2.5-leaf stage were transplanted. Plants were grown by placing the plants in a greenhouse at 25 to 30°C, and on the third day after sowing, a diluted drug solution was dropped onto the water surface using a volumetric pipette at a predetermined dose. Three weeks after dropping the chemical solution, the herbicidal effect on rice and various weeds was investigated according to the criteria of Test Example-1. The results are shown in Table 6.

(Hereafter, margin) Chapter 1 Table A compound of the present invention represented by the general formula [■].

In the table, the axis is a methyl group, Et is an ethyl group, Pr is a normal propyl group, Pr' is an isopropyl group, nu is a normal butyl group, Bu' is a secondary butyl group, BuL is a tertiary butyl group, and ph is a phenyl group. shows.

NoR Table 1 (continued) XtX Properties (physical properties) General formula (I) Nuclear magnetic resonance spectrum data of representative compounds of the present invention shown in Table 4.17 (s, 3H), 7.00 ~7.70 (m,
68).

10.05 (bs, 1) 1) 3.70 (s, 311), 4.10 (s, 311),
6.70 (s, 1H).

3.73 (s, 311), 3.77 (s, 310.
4.13 (s, 3tl).

6.72(s, It(), 6.513~7.20(
m, 411).

8.00 (bs, 18) 1.33 (t, J=6.5Hz, 311), 3.87 (
q, J=6.5)12,211), 4.10(s,
3H), 6.70 (s, 18).

6.38-7.20 (m, 411), 7.83 (b
s, LH) Table (continued) 1.30 (t, J=6Hz, 611), 3.90 (
q, J=6Hz211), 4.00(q, J=6)1
z, 2) 1), 4.13 (s.

1.00 (t, 3tl, J=6.511z),
1.43-2.13 (m, 21+), 3.90 (t
2H, J=6.5Hz), 4.20(s, 311),
6.85 (sJll), 7.25 (s, 111
).

5.13-5.63 (m, 2H), 5.73-6.
37 (m.

1ft), 6.88(s, LH), 7.28(
s, III).

1.28 (d, J=6Hz, 611), 4.12 (
s, 311).

4.45 (7th, J=611z, 1)1),
6.45-7.301H).

7.47 (s, 1ll).

7.00-8.37 (m.

4.15 (s, 3H), 5.00 (s, 2H),
6.70 (s.

IB), 7.21 (s, 511), 7.58 (
, bs, IH).

6.52-7.73 (m, 411) 2.32 (m, 211), 3.60 (t, 21
1. J=611z), 4.10(t, 2H, J=
6Hz), 4.22 (s, 311), 6.82 (s.

4.32(q, 21(, J=7Hz).

4.37 (Q, 211.J=8112).

6.98 (s, III).

7.45 (s, III).

Table 2 (continued) Table 2 (continued) Compound of the present invention' H-NMR δ value (ppm) Solvent (C
DCl *) Nα 2.60 (s, 3H), 4.20 (s, 3H),
7.00(s, 1t().

6.9 (1-8.30 (m, 4) 1), 8.63 (
bs, III) 2.93 (s, 68), 4.18 (
s, 31), 6.83 (s.

III), 6.33-7.37 (m, 4H),
7.68 (bs, IH) 1.40 (t, J=6.5Hz
, 38), 1.49 (t, J=6.5Hz, 311),
4.01 (Q, J=6.511z, 2)1), 4.
61 (q, J=6.5Hz, 2H), 6.06-7.3
0 (m, 4H).

6.77 (s, IH), 7.54 (bs, 111)
1.39 (t, J=6.5Hz, 3H), 1.48
(t, J=6.5tlz.

3H), 1.50(t, J=6.511z, 311
), 4.02 (qJ=6.5Hz, 2H, 2tl)
, 4.11' (q, J=6.5Hz, 2tl).

6.65～? , OQ(m, 21(), 6.79(s
, l1l).

7.16 (d, J=211z, IH), 7.7
3 (bs, l1l) 1.32 (d, J=6.5Hz
, 611), 1.48 (t, J=6.5) 1z, 3H)
, 4.59 (m, 3H), 6.53-7.30
(m, 4H), 6.78 (s, IH), 7.5
7 (bs, 1tl) Compound of the present invention' H-NMR δ value (ppm) Solvent (CDCi: l) Nα Hz), 1.67 to 2.23 (m, 2H), 4.0
0 (q.

2H, J=7) 1z), 4.53(t, 2H, J=7
11z), 6.8(s, 18), 7.2(s, 111
), 6.5-7.43 (m.

31(), 7.62(bs, 1t()1.38(t
, 3H, J=711z), 1.50(d, 6H, J
=7)1z).

3.98(q, 21(, J=711z), 5.08~
5.72 (m.

1ft), 6.30-7.40 (m, 511), 7.
57 (bs, IH) 1.50 (t, 3H, J=711z
), 4.10(q, 21LJ=7Hz), 5.47(
Q, 2tl, J=9Hz), 7.10(s, 1ll).

6.70-7.63 (m, 411), 7.85 (bs
, LH) 1.37 (d, 6H, J=61(z), 4
．． 40-4.90 (m.

1tl), 5.50(q, 21LJ=81+z),
7.08 (s, IIIL6.67-7.67 (m, 41
1), 7.95 (bs, III) 1.42 (t, 3
H, J=711z), 3.98(q, 2H, J=7H
z), 4.15 (s, 311), 6.43-7.3
3(Ill.

41(), 8.07(bs, 1ll) J=711z
), 4.32 (s, 3H), 7.07 (s, IH)
.

4.30-4.85 (m, LH), 6.58-7.4
8 (m.

1.45 (t, 3H, J=7.2Hz), 4.13 (
q, 211. J=7.2Hz), 4.35(s, 31
1), 6.68 to 7.721.45 (t, 3H, J=
6.5Hz), 1.47(t, 3H.

J=6.511z), 4.16(q, 2H, J=6.
5Hz).

4.20 (q, 2H, J=6.511z), 4.32
(s, 31().

7.10(3,1)1), 7.00~7.70(m,
3H).

8.45 (bs, LH) Table 2 (continued) Compound of the present invention 'l (-NMR δ value (ppm) Solvent (
coc 13) Nα 1.33 (d, 68.J=6Hz), 4.15 (s
, 311).

4.25-4.8 (+n, 18), 6.50-7.
40 (m.

・4tl), 8.08 (BS, LH) 2.45
(s, 311), 4.15 (s, 3H), 6.
70-7.58 (m, 411), 8.08 (bs,
IH) 1.42 (t, 3tl, J=711z), 4
．． 03 (s, 311).

4.07 (q, 2H, J=711z), 6.53~
7.63 (m.

4H), 7.20 (s, 1ll) 1.33 (d, 6H, J=6Hz), 4.13 (s
, 3H).

4.27-4.83 (m, IH), 6.53-7.
5 (m.

4H), 9.27 (BS, LH) No. table General formula [■] The compound of the present invention represented by In the table, Arms are methyl groups, Et is an ethyl group, Pr is quota lepropyl group, Pr' is an isopropyl group, Bu is quota rubyl group, Bu' is a secondary butyl group, uL teeth No. Table (continued) No. Table (continued) R' Character: 0 lucid No. Table (continued) No. Table (continued) No. Table (continued) No. Table (continued) Cut ×1 ×2 Properties tw-b No. Table (continued) ×3 Characteristics (raccoon dog) No. Table (continued) No. Table (continued) enemy ×2 Properties (glue D I Properties (- No. Table (continued) No. Table (continued) ×1 χ3 Properties (cherry blossoms) I Properties (轡D No. Table (continued) No. Table (continued) I ×3 Characteristics (raccoon dog) ×3 Properties (things) No. Table (continued) No. Table (continued) x' Properties (Shu 0 l ×2 ×3 Properties (shelf 9 No. Table (continued) No. front α selling) Z Properties G-0 No. Table (continued) No. Table (continued) I Properties (starchy) Properties (cherry blossoms) No. Table (continued) No. Table (continued) No. Table (continued) No. Table (continued) ×2 Physical properties No. Table (continued) No. Table (continued) R' ×1 t ×3 Properties (vAsu) R+ turmoil x′ χ3 Properties (N!t) t CO 11klclOcI Shame Cl0II Shame Cl0CI No. Table (continued) No. Table (continued) enemy ×3 Properties (handling D No. Table (continued) No. Table (continued) Characteristic Qpo I ×2 Properties Q-9 No. Table (continued) No. Table (continued) R' I Properties (of the shelf) Properties (of the shelf) No. Table (continued) No. Table (continued) turmoil X+ ×3 Properties (handling) R+ circle I ×2 ×3 Character ■ God D t r ω sugar Me t r Bu Bu No. Table (continued) No. Table (continued) turmoil Properties (shock D χ1 Properties (handling D No. Table (continued) No. Table (continued) ll I Properties (Sakura's) I ×2 X'3 Properties (shelf) No. Table (continued) No. Table (continued) x′ Characteristic Po〇 ×1 ×3 Properties (cherry blossoms) No. Table (continued) No. Table (continued) turmoil ×1 Properties (handling) I ×2 property side No. Table (continued) No. Table (continued) enemy ×2 Properties (of the shelf) Properties (shelf D No. Table (continued) No. Table (continued) enemy X″ Properties (starchy) ga X′ Properties (of the shelf) t Fall Et Et Et No. Table (continued) t Properties (shelf) No. Table (continued) t X″ nature (reward) No. table No. table

Claims (1)

[Claims] (I) General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc.▼ [I] [In the formula, R is a hydrogen atom or an optionally substituted alkyl having 1 to 6 carbon atoms group (this substituent has 1 carbon number)
~4 alkoxy group and halogen atom. ) is shown. R^1 is a hydrogen atom, a halogen atom, a nitro group, or an optionally substituted alkyl group having 1 to 6 carbon atoms (this substituent includes an alkoxy group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms,
4 represents an alkylthio group and a halogen atom. ) is shown. X^1, X^2 are hydrogen atom, halogen atom, carbon number 1~
6 alkyl group, haloalkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, haloalkoxy group having 1 to 6 carbon atoms, phenoxy group, aralkyloxy group, alkoxyalkoxy group, having 2 to 6 carbon atoms Alkenyloxy group, alkynyloxy group having 2 to 6 carbon atoms, alkylthio group having 1 to 6 carbon atoms, haloalkylthio group having 1 to 6 carbon atoms, alkylsulfonyl group having 1 to 6 carbon atoms, haloalkyl having 1 to 6 carbon atoms It represents a sulfonyl group, an alkoxycarbonyl group having 1 to 6 carbon atoms, an alkylcarbonyl group having 1 to 6 carbon atoms, a nitro group, a cyano group, or an alkylamino group having 1 to 6 carbon atoms. X^3 represents a hydrogen atom, an alkoxy group having 1 to 6 carbon atoms, or a haloalkoxy group having 1 to 6 carbon atoms. W represents an oxygen atom or a sulfur atom. Moreover, X^1 and X^2 can be combined with each other to form a 5-membered ring or a 6-membered ring containing 1 to 2 oxygen atoms. ] A pyrazole carboxamide derivative represented by. (2) A herbicide containing one or more pyrazole carboxamide derivatives according to claim (1) as an active ingredient.