JPH01207207A - Herbicide containing pyrazolecarboxylic acid amide derivative as active component - Google Patents

Abstract

PURPOSE:To obtain a herbicide having strong herbicidal activity against various kinds of weeds, exhibiting excellent effect especially against perennial gramineous weeds, safe to rice plant which is an important crop and effective at a low rate of application, by using a pyrazolecarboxylic acid amide derivative as an active component. CONSTITUTION:The objective herbicide contains a pyrazolecarboxylic acid amide derivative of formula I (R is phenyl or 1-4C alkoxy which may be arbitrarily substituted with F or Cl, N-substituted pyrazole residue, N-substituted imidazole residue or N-substituted triazole residue) as an active component. The compound is mixed with a carrier such as clay or talc, a surfactant, etc., and used in the form of solution, emulsifiable concentrate, etc. It can be applied even to a playground, vacant land, etc., as well as agricultural or horticultural field. The preferable rate of application is about 0.1-5kg per 1ha. The active component of formula I can be synthesized e.g., according to the reaction formula.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a herbicide containing a pyrazolecarboxylic acid amide derivative as an active ingredient, and is particularly applicable to paddy fields,
Effective as a herbicide for upland fields.

[Conventional technology and issues]

Conventionally, many herbicides have been put to practical use in order to protect important crops such as rice, soybeans, wheat, corn, cotton, and beets from weeds and to increase the productivity of these important crops.

Particularly in recent years, with the global population increase, it is inevitable that the productivity of important crops will have a direct impact on the world food economy. For this reason, there is an increasing need for farmers to develop herbicides that can efficiently kill weeds that get in the way of growing important crops.

There is a strong desire to develop such herbicides that meet the following requirements. It has a moderate residual effect, requires fewer chemical treatments (this is also important for saving labor in weed control work), has a wide herbicidal spectrum, and is effective against crops at the same time. Those that are highly safe, those that are highly effective against perennial weeds that are difficult to control (many perennial weeds are among the world's major weeds), and those that have high herbicidal effects at low doses (especially those that protect the environment) It is desirable to kill weeds by spraying as low a dose as possible. However, existing herbicides do not necessarily meet all the conditions.

On the other hand, as amide-substituted acetonitrile derivatives, herbicides are disclosed in JP-A-57-167978 and JP-A-62-106093. For example, JP-A-62-106
Publication No. 093 describes that pyridinecarboxylic acid derivatives can be used as active ingredients of herbicides, but these compounds have insufficient herbicidal effects and are not necessarily excellent as herbicides for paddy and field fields. I can't say that it is.

[Means to solve the problem]

In view of this situation, the present inventors, with the aim of overcoming the drawbacks of the prior art described above, have developed a method that exhibits selectivity for important crops and has excellent herbicidal effects at low doses. As a result of many years of continuous research to develop herbicides, the formula (
1) [In the formula, R is a phenyl group which may be optionally substituted with a fluorine atom and/or a chlorine atom, and has a carbon number of 1 to 4
represents an alkoxy group, N-substituted virazole group, N-substituted imidazole group or N-substituted triazole group. ]
Herbicides containing pyrazole carboxylic acid amide derivatives as an active ingredient have a strong herbicidal power against many weeds, especially perennial grass weeds, in soil treatment, foliage treatment, or hot water treatment. The present invention was completed based on the discovery that the present invention has excellent herbicidal effects on rice, which is an important crop, and is highly safe.

Next, synthesis examples of these pyrazolecarboxylic acid amide derivatives will be specifically described as reference examples, but the present invention is not limited thereto.

Imperial Review ■2-Ethoxy-2-((1-methylpyrazol-5-yl)carbonylaminocoacetonitrile (Compound No.
Synthesis of 7) 5.09 g of acetic acid was added.

After 1 hour, the temperature was raised to room temperature and poured into ice water. After extraction with ethyl acetate, the mixture was washed with water and saturated brine, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain a crude product. This was purified by column chromatography (developing solvent chloroform),
1.05 g of the target compound was obtained as white crystals.

Melting point 61-63'C' +1-NMR (CDCf3>δ: 1.15(3
11,t, J=711z), 3.63(2+1°Q,
J=7Hz), 4.07(3H,s), 6.08(1)
1. d, J=9Hz), 6.71 (LH, d, J=
2Hz), 7.39 (LH, d, J=2Hz), 8.4
7 (Ill, d, J = 9tlz) 奎子±二l 2-((1-methylpyrazol-5-yl)carbonylaminoco-2-phenylacetonitrile (compound Nα1
Synthesis of t3N A mixture of 1.52 g of 1-methyl-5-pyrazolylcarboxylic acid and 15 ml of thionyl chloride was refluxed for 3 hours, and thionyl chloride was distilled off to obtain an acid chloride. Phenylglycinonitrile hydrochloride 2. Olg, triethylamine2.
40 g was added to the mixture of acetonitrile 15 at below 5°C. After 1 hour, the temperature was raised to room temperature, and ice water was added. After extraction with ethyl acetate, the mixture was washed with a saturated aqueous sodium bicarbonate solution, water, and saturated brine, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain a crude product. This was purified by column chromatography (developing solvent chloroform) to obtain the target compound 0.
, 47 g were obtained as white crystals.

Melting point 130.5-133.5°C 'II-NMR (d, -DMSO) δ: 4.12 (3
H, s), 6.26 (IH, d, J=611z), 6
．． 91 (LH, d, J = 1.511z), 7.13-7
．． 69 (6u.

1 2-((1-methylpyrazol-5-yl)carbonylamino)-2-(2,5-difluorophenyl ) Synthesis of acetonitrile (compound No. 4) hN The target compound was obtained by reacting with 2,5-difluorophenylglycinonitrile in the same manner as in Reference Example-2.

Melting point 117-119°C Jl-NMR (d6-DMSO) δ: 4.12 (3
H, s), 6.38 (IH, d, J=6 tl z )
, 6.93 (111, d, J=1.5Hz), 7.38
(IH, d, J=1.511z), 6.88-7.58
(3H, m), 9.48 (Ill, br, d.

Synthesis of 2-((1-methylpyrazol-5-yl)carbonylamino)-2-(1-pyrazolyl)acetonitrile (Compound No. 11) 2-((1-methylpyrazol-5-yl) 5-yl)carbonylamino)-2-(1-pyrazolyl)acetamide 0.50 g,) ethylamine 0
．． -20 g in a mixture of 41 g and 8 d of tetrahydrofuran.
0.85 g of trifluoroacetic anhydride was added at a temperature below C. After 1 hour, the temperature was raised to room temperature and poured into ice water. After extraction with ethyl acetate, the mixture was washed with moderate brine, dried over anhydrous sodium sulfate, and the solvent was distilled off. A crude product was obtained.This was purified by column chromatography (developing solvent: chloroform) to obtain 0.28 g of the target compound as white crystals.

Melting point 169-171"C'II-NMR (d, -DMSO) δ: 4.09 (3
H, s), 6.29 (IH, t, J=2Hz), 7.0
5 (111, d, J = 2 Hz), 7.38 (III, d
, J=2Hz) ,'1.42(IH,d, J=8Hz
>, 7.55 (IH, d, J = 2Hz), 7.86 (
IH, d, J = 211z), 10.42 (IH, d, J
=811z) Next, examples of compounds included in the present invention are shown in Table 1, including the compounds synthesized in the reference example, but the present invention is not limited thereto.

Table 1 lh R No, R melting point [°C] 1 phenyl 130.5-133.522
-chlorophenyl 32-fluorophenyl 42.5-difluorophenyl 117.
0~119.054-fluoropheny1 60CH:1 70CzHs 61.0~63.080CII
□CH2Cl+.

90CII(CHa)! 100C112C112CH2CIh Table 1 - Continued When applying the compounds of the present invention as herbicides, they are generally applied with a suitable carrier, such as a solid carrier such as clay, talc, bentonite, diatomaceous earth, white carbon, or water, alcohols (isopropanol, phthanol, etc.). , benzyl alcohol, furfuryl alcohol, etc.), aromatic hydrocarbons (toluene, xylene, etc.), ethers (anisole, etc.), ketones (cyclohexanone, isophorone, etc.), esters (butyl acetate, etc.), acid amides ( N-
methylpyrrolidone, etc.) or halogenated hydrocarbons (chlorobenzene, etc.), and optionally surfactants, emulsifiers, dispersants, penetrants, spreading agents, and thickeners. , anti-freezing agents, anti-caking agents, stabilizers, etc. are added to produce liquids, emulsions, wettable powders, flowables,
It can be put to practical use in any dosage form such as powder or granules.

In addition, the compound of the present invention may be used with other herbicides, various insecticides, fungicides, plant growth regulators,
It may be used in combination with synergists, antidotes, etc.

As for the type of herbicide to be mixed, for example, the Farm Chemicals Handbook (Farm Chemi-c
There are compounds described in the 1987 edition of ``Als Handbook'', 1987 edition. The amount of the applied drug varies depending on the application situation, application time, application method, cultivated crop, etc., but in general, the amount of active ingredient is 0.01 per hectare (ha).
~5 kg is appropriate.

Next, specific formulation examples of formulations using the compounds of the present invention will be shown. However, the formulation examples of the present invention are not limited to these only. In addition, in the following formulation examples, "parts" mean parts by weight.

By condition ↓ Hydrating agent Compound of the present invention Nα1 ・・・・・・・・・・・・・・・
・・・・・・ 45 parts or more are uniformly mixed and ground to make a wettable powder.

"Example F in Japan" - Hydrating agent Compound of the present invention Nα4 ・・・・・・・・・・・・・・・
・・・・・・ 45 parts or more are uniformly mixed and ground to make a wettable powder.

ΣKin■Yu Hydrating agent Compound of the present invention Nα7 ・・・・・・・・・・・・・・・
・・・・・・ 45 parts or more are uniformly mixed and ground to make a wettable powder.

R Gold ■ Earth Wettable powder Compound of the present invention Nα11・・・・・・・・・・・・・・・
... 50 parts or more are uniformly mixed and ground to make a wettable powder.

Lipstick emulsion Compound N of the present invention [lil...
・・・・・・・・・ Part 8
・・・・・・・・・・・・・・・・・・・・・ 71
Part Isophorone ・・・・・・・・・・・・・・・・・・
... 15 parts or more are mixed uniformly to form an emulsion.

Flowable agent Compound of the present invention Nα11・・・・・・・・・・・・・・・
・・・・・・ 35 parts ethylene glycol (antifreeze agent) ・・・ 8 parts water ・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
... 28.5 parts or more are mixed uniformly to form a flowable agent.

Mouth-filling granules Compound No. 11 of the present invention
・・・・・・・・・ Part 1 bentonite ・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・ 55
Part Tarri・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・ After uniformly mixing and pulverizing 44 parts or more, add a small amount of water and stir and knead.
It is granulated using an extrusion granulator and dried to form granules.

When used, the above-mentioned wettable powders, emulsions, and flowable preparations are diluted 50 to 1000 times with water and sprayed at a concentration of 0.01 to 5 kg of the active ingredient per hectare (ha).

In addition to agricultural and horticultural fields such as fields, paddy fields, orchards, the compounds of the present invention can also be applied to control various weeds in non-agricultural lands such as playgrounds, vacant lots, and railway edges, as well as pastures and lawns. The dosage varies depending on the application situation, application period, target grass species, cultivated crops, etc., but in general, a rate of about 0.1 to 5 kg per hectare (ha) is appropriate.

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

Wiping ± two tops Weeding effect test by soil treatment Vertical 15cm+*
, put sterilized diluvial soil in a plastic box 22 cm wide and 6 cm deep, and grow wild wild grass, crabgrass, cyperus, and
The soil was mixed with a mixture of seedlings such as dogwood, leafminer, and dogwood, and the soil was covered to a depth of about 1 cm, and then the active ingredients were uniformly spread over the soil surface in a predetermined ratio. The chemical liquid was prepared by diluting the wettable powder, emulsion, or flowable agent of the formulation example described above with water and spraying the mixture over the entire surface with a small sprayer. Four weeks after spraying the chemical solution, the herbicidal effect on various weeds was investigated according to the following criteria.

The results are shown in Table 2.

Judgment Criterion 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% 1...Weed killing rate 5-20% 0...Weed killing rate 5% or less However,
The above-mentioned weed killing rate was determined by the following formula by determining the above-ground fresh grass weight in the chemical-treated plot and the above-ground fresh grass weight in the non-treated plot.

For trial 1, weeding effect test by stem and leaf treatment, 15 cm long,
Sterilized diluvial soil was placed in a plastic box measuring 22 cm wide and 6 cm deep, and seeds of Japanese wild grass, crabgrass, Japanese cyperus, Japanese dogbane, Japanese leafminer, and Japanese dogwood were sown in spots, and covered with soil to a depth of about 1 cm. When each plant reached the 2-3 leaf stage, the active ingredient was uniformly sprayed onto the stems and leaves so that the amount of the active ingredient was at a predetermined ratio.

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

Four weeks after spraying the chemical solution, the herbicidal effect on various weeds was investigated according to the criteria of Test Example-1. The results are shown in Table 3.

Test 1 Butsuji” - Herbicidal effect test under flooded conditions 1150
After placing alluvial soil in a 00 are Hugner pot,
Add water and mix to create freshwater conditions at a depth of 2 cm. 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. The pots were placed in a greenhouse at 25 to 30°C to grow the plants, and on the third day after sowing, a diluted drug solution was dropped onto the water surface using a measuring 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 4.

jJsMJL2'Yu Herbicidal effect test on perennial grass weeds Sterilized diluvial soil was placed in a plastic box measuring 15 cm in length, 22 cm in width, and 12 cm in depth, and tubers of johnson grass and grasshoppers cut into lengths of approximately 6 cm were placed in a plastic box measuring 15 cm in length, 22 cm in width, and 12 cm in depth. The underground rhizomes of Gyogishiba were buried to a depth of about 3 cm. When each plant reached the 3rd to 5th leaf stage, the active ingredients were uniformly sprayed onto the stems and leaves using a small spray so that the amount of the active ingredient was in a predetermined ratio.

Thirty days after spraying the chemical solution, the herbicidal effect on various weeds was investigated according to the criteria of Test Example 1. The results are shown in Table 5.

Table 2 The symbols in the table have the following meanings. Nobie (Nobie), Nobie (Nobie)
K (Japanese cyperus), K (Japanese cyperus)
, dan (Hakitamegiku), ± (Doggarashi).

Table 3 The symbols in the table have the following meanings. -N (wildflower), 琶 (blackfish), K (cyperus cyperus), and (Japanese cyperus), D (Japanese leafminer), and soil (Japanese cyperus).

[Margin below]

Table 4 I Sa Ne Table 5 However, the grass species in the table are as follows.

(1): Johnson grass, (2): Shiba wheat, (3)
: Gyogishiva Hisashi, Comparative Compound A is patent applicant Nissan Chemical Industries, Ltd.

Claims (1)

[Claims] Formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R is a phenyl group which may be optionally substituted with a fluorine atom and/or a chlorine atom, the number of carbon atoms 1-4
represents an alkoxy group, an N-substituted pyrazole group, an N-substituted imidazole group or an N-substituted triazole group. ]
A herbicide characterized by containing a pyrazolecarboxylic acid amide derivative represented by: as an active ingredient.