JPS6051175A - Pyrazole derivative and selective herbicide - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (X is halogen or nitro; Y is H, lower alkyl or halogen; Z is halogen or methanesulfonyl) or its organic acid ester. EXAMPLE:4-(2,4-Dichloro-3-methylbenzoyl)-1-methyl-5-hydroxypyrazole. USE:A selective herbicide. Usefel as a safe herbicide for plowed land having strong herbicidal activity against gramineous weeds, broad-leaved weeds and nut grass, and free from phytotoxicity to corn, sorghum, etc. It exhibits high herbicidal activity to the harmful weeds in paddy field, such as flatstage, bulrush, etc. in addition to barnyard grass, etc. PREPARATION:The compound of formula I can be produced in high yield, by the condensation reaction of the benzoyl halide of formula III (Q is halogen or OH) and 5-hydroxy-1-methylpyrazole of formula II derived from diethyl ethoxymethylenemalonate and methylhydrazine.

Description

[Detailed description of the invention] Oh.

(In the formula, xf′i represents a halogen atom or a nitro group, Y represents a hydrogen atom, a lower alkyl group, or a halogen atom, and 2 represents a halogen atom or a methanesulfonyl group.) or its organic compound A novel pyrazole derivative which is an acid ester and one of the compounds or ij
The present invention relates to a selective herbicide containing two or more types of herbicides as active ingredients.

BACKGROUND ART A wide variety of herbicides have been put into practical use over many years of research and development, and these herbicides have contributed to saving labor in weed control operations and improving the productivity of agricultural and horticultural crops.

Even today, there is a demand for the development of new chemicals with more excellent herbicidal properties, and 9% of agricultural and horticultural herbicides are needed to selectively target only target weeds without causing harm to cultivated crops and at low dosages. Although it is desirable to be able to control herbicidal herbicides, existing agents do not necessarily have suitable herbicidal properties.

While conducting research on the herbicidal properties of various organic compounds for the purpose of developing useful herbicides, the present inventors discovered that the above-mentioned compound was effective against grasses (Poaceae and Cyperaceae) and various broad-leaved weeds. A useful crop that has excellent herbicidal efficacy against plants.

The present invention was completed with the knowledge that M. and T. are substantially harmless to cultivated crops such as corn and turgid.

This compound shows strong herbicidal activity in both soil treatment and soil mixing treatment, and on the other hand, it has a strong herbicidal activity on cultivated crops such as corn and vine gum, regardless of soil destruction treatment and soil mixing treatment. It shows no phytotoxicity and has a high degree of selectivity, making it extremely effective for controlling weeds during the cultivation of these crops.

Namely, the noxious weeds that occur during the cultivation of corn and trumpet;

It exhibits strong herbicidal activity against Japanese fir tree, Japanese grasshopper, Japanese sedge, etc. Particularly herbicidal activity against grasshopper species.
- is extremely high and extremely unique. Conventionally, the nihatriazine herbicide atrazine and the acid anilide herbicides lasso and puer have been used when cultivating corn and trumpet gum. However, although atrazine exhibits high activity against broad-leaved weeds, it has low activity against Poaceae and is extremely low in activity against Poraceae.

On the other hand, lasso and dual have high activity against grasses, but low activity against broad-leaved weeds.

In addition, activity 4 against Japanese porphyry is extremely insufficient. Therefore, it has been extremely difficult to eradicate all weed species with a single chemical treatment.

As a result of various studies, the present inventors have discovered that the compound of the present invention is effective against a wide range of weeds, and among these weeds, it is extremely effective against the perennial weed, Chimney spp., which has been particularly difficult to control in the past. Based on these findings, we have completed the present invention.

Furthermore, the compound of the present invention has the effect that it has no phytotoxicity to corn and turgid and can be used safely.

The compound of the present invention has the general formula (1): (wherein, X
, Y, ZFi, same as above. ) or a pyrazole derivative represented by its organic acid ester, and its chemical structure is characterized by: The 5th position of the pyrazole ring is a hydrogen atom, and the 5th position is a hydroxyl group or an organic acid ester thereof.

Hitherto, several compounds have been known as pyrazole derivatives having herbicidal activity.
664B and Japanese Patent Application Laid-open No. 54-41872, 4
- Benzoyl derivatives have been described to be useful as herbicides.

These pyrazole derivatives have been put to practical use.

Only virazolate (common name) represented by Compound A is commercially available.

1 In the pyrazole derivative described in the above-mentioned Japanese Patent Application Laid-Open No. 54-41872, all the 5-positions of the pyrazole ring of the compound represented by the above formula (1) are only CR2 groups.

Furthermore, in the pyrazole derivatives described in the above-mentioned Japanese Patent Publication No. 54-5664B, the 3rd position of the pyrazole ring of the compound represented by the formula (I) is mostly a lower alkyl group, and the 5th position is a lower alkyl group. The substituents are OH, SH, their salts, and esters with specific organic acids. Among these, when the 5th position is a hydrogen atom, only the - example is specifically described as an example, as shown below.

C (hereinafter referred to as compound B) However, this compound B is
As is clear from the description of the biological test data in Publication No. 8, the herbicidal activity is inferior to that of the commercially available Compound A.

The present inventors conducted a comparative test with the compound of the present invention, Compound A, and Compound B, and confirmed that the compound of the present invention had far superior herbicidal activity.

A large number of pyrazole conductors have been synthesized in the past.

Even though herbicidal activity tests were conducted.

Compound B was the only compound in which the 5th position of the pyrazole ring was a hydrogen atom.

The reason for this is that the synthesis of compounds having a substituent such as alkyl at the 5-position (5-position alkyl derivatives) is relatively easy, but when the 3-position is a hydrogen atom, the synthesis is extremely difficult. It was thought that this was due to the fact that the herbicidal activity was lower than that of the 5-position alkyl derivative, and that it was less practical.

As a result of various studies on compounds in which the 5-position of the pyrazole ring is a hydrogen atom, the present inventors found a method that can be easily synthesized, and also conducted various studies on the substituted moiety at the 5-position. The compound of the present invention represented by the general formula (r) has an exceptionally strong herbicidal power against grass weeds, broad-leaved weeds, and also against grass weeds, and also has high safety against Vcl--Morochoa and Tsuruga, It was discovered that it has extremely excellent properties as a field herbicide.

In addition, the compound of the present invention not only has high herbicidal activity against harmful weeds found in rice fields, such as Japanese millet, Japanese snail, Japanese azalea, Japanese grass, and other weeds.

It has been found that this product has extremely high herbicidal activity against weeds that have been extremely difficult to control, such as Japanese cypress, Japanese firefly, and Japanese black grub.

This excellent effect on Mizugaya IJ fido is due to the fact that the 5th position of the pyrazole ring is a hydrogen atom in terms of its chemical structure. It was necessary to have a substituent at the V position at the same time.

In this way, the compounds of the present invention are highly effective against perennial weeds such as Japanese barnyard grass and broad-leaved grasses, which are particularly difficult to control and for which there are almost no effective herbicides available. It has extremely excellent performance as a herbicide.

Next, one of the compounds of the present invention can be easily synthesized, for example, by the following reaction formula.

(11c2 H2OCH=C(CoOO2H5) 2
+CHs NHNH2 [In the formula, Q represents a halogen atom or a hydroxyl group, and X, Y and 2 have the same meanings as above. ] Further, by condensing Ic or compound (b)Fi with, for example, a halogenide of a suitable organic acid in a conventional manner, it can be easily converted into an ester of a suitable organic acid.

Reaction formula (1) Using diethyl malonate and methylhydrazine as raw materials, 4-carboethoxy-5
-Hydroxy-1-methylpyrazole is synthesized and then hydrolyzed and decarboxylated to completely form 5-hydroxy-1-methylpyrazole (a).

Further, compound (b) can be easily synthesized using compound (a) as a raw material according to reaction formula (2). - For example, compound (a) may be treated with a dehydrogenating agent (preferably sodium hydroxide or potassium hydroxide).

In one reaction, various benzoyl halides are reacted in the presence of sodium carbonate, triethylamine, pyridine) in an inert solvent to form esters, which are then rearranged to form esters (
b) can be obtained in high yield. As a solvent for the esterification reaction, for example, dioxane, acetonitrile, benzene, toluene, chloroform, etc. can be used alone, but 1, for example, water-toluene, water-
Two-phase systems such as chloroform can also be utilized.

A Lewis acid such as aluminum chloride, tin chloride, zinc chloride, or a base such as calcium hydroxide, potassium carbonate, IJium carbonate, etc., without a solvent for the rearrangement reaction or in a solvent inert to the reaction (preferably μ dioxane, acetonitrile, etc.) can be easily progressed in the presence of

Next, a method for producing one of the compounds of the present invention will be illustrated by way of specific examples. However, the present invention is not limited only to these examples.

Iskan IJ1 Yu Synthesis of 1-methyl-5-hydroxypyrazole Ethanol 150rn1. and ethoxymethylenemalonic acid diethyl ester 108p (0.5 mol) were cooled to below 0°C, and methylhydrazine 2!+f (0.5 mol) was added dropwise while keeping the reaction temperature below i0''C. After the dropwise addition was completed, the mixture was stirred at room temperature for 1 hour and then refluxed for 1 hour.Next, 200 grams of concentrated hydrochloric acid was added to this reaction mixture and refluxed for 2 hours.After the reaction was completed, the reflux condenser of this reactor was separated from water. After replacing the apparatus and adding butanol to the reaction mixture, azeotropic dehydration was performed. After completion of dehydration, butanol was distilled off under reduced pressure, and the residue was recrystallized with isopropyl alcohol to obtain the title target compound 3B7 (0, 38 moles)
was obtained as a hydrochloride (yield: 76 cm), melting point: 155-147
℃.

] - Nine Synthesis of 4-(2,4-dichloro-6-methylbenzoyl)-1-methyl-5-hydroxypyrazole (Compound No. 5) 1-Methyl-5-hydroxypyrazole hydrochloride 13,5
F (0.1 mol) to potassium hydroxide 11.22 (0
After dissolving 20 g of chloroform (2 mol) in an aqueous solution at 0°C, 50 g of chloroform was added to form two layers.

Furthermore, 22.4 y (0.1 mol) of Ic, 2,4-dichloro-3-methylbenzoyl chloride was added dropwise.

The reaction was allowed to proceed at room temperature for 2 hours. The chloroform layer was separated from the reaction solution, and after drying, the solvent was distilled off under reduced pressure to obtain solid iC,1,4-dioxane 25d and potassium carbonate 27
．． 67 (g, 2 mol) was added and heated to 100-120°C. During the reaction, after a solid was obtained at about 1 hour...
Distill the solvent and add 30ml of isopropyl alcohol.
Add 1.

It was refluxed for 50 minutes. Pour the resulting powdered solid into ice water;
After dissolving, acidify with hydrochloric acid, and dry the generated solid separately.
Recrystallization from 95% ethanol yielded 2022 of the desired product.

(Yield: 71 cm) Melting point: 131.0-135.0°C 'H-NMR (C!DOf, , δ, ppm):
2. so (3n, S), 366 (5H.

S), 7.10-7.46 (5H), 8.16 (I
Synthesis of 4-(2,4-dichlorobenzoyl)-1-methyl-5-benzoyloxypyrazole (Compound No. 11) 4-(2,4-
2.71 ji' (0.01 mol) of dichlorobenzoyl)-1-methyl-5-hydroxypyrazole and 1.71 ji' (0.01 mol) of triethylamine. o i y (o, .

1 mol) in 50 ml of anhydrous benzene, and then a solution of 1.417 (Q, 01 mol) of benzoyl chloride in 5d of anhydrous benzene was added dropwise with stirring at room temperature.
It was then heated to 40-50°C for 30 minutes. After cooling the reaction mixture, the generated salt was separated and benzene was distilled off under reduced pressure. The obtained oil was purified by gel column chromatography (eluent: benzene) to obtain 3262 of the desired product. (Yield 87%) 9H) Factor] L Example 4 Synthesis of 4-(2,4-dichloro-3-methylbenzoyl)-1-methyl-5-(4-methylbenzenesulfonyloxy)pyrazole (Compound No. 19) 4-(2,4-dichloro-5-methylbenzoyl)-1
-Methyl-5-hydroxypyrazole 145p (300
5 mol), triethylamine 051 f t o, o
p-Toluenesulfonic acid chloride 09571 &: was added to a solution of 0 smol) in anhydrous benzene, and the mixture was stirred at room temperature for 1 hour. After the generated salt was distributed from house to house, the method of Example 5
By performing the same post-treatment and purification as above, the target product 'f
:2. Of got it.

(Yield 91%) 'H-NMR (δ, ppm, CD0j+,):
2.40 (5H1S L 2.45 (5H,S).

! 1.77 (3H,S), 6.89-7.87 (
7H) Example 5 Synthesis of 4-(2,3,4-)dichlorobenzoyl)-1-methyl-5-methanesulfonyloxypyrazole (Compound No. 20) 4-(2,5,4-)dichlorobenzoyl )-1-methyl-5-hydroxypyrazole1. sss! (
0005 mol), triethylamine 05t? (00
05 mol) in 20 mUffJ solution of anhydrous benzene.

Methanesulfonyl chloride 0.579 (Q, 00
5 mol) was added dropwise with stirring. Thereafter, the reaction and post-treatment were carried out in exactly the same manner as in Example 4 above.

172 pieces of the target product were obtained. (Yield: 89cm) Melting point = 152-155°G'H-NMR (δ, 1)I)m, 0DOA):
5.59 (3)1. El), 3.89 (5H.

S), 71s~7.58 (5H) Implementation fl160.0-diethyl-〇-(4-(2,4=
Synthesis of dichlorobenzoyl)-1-methyl-5-pyrazolyl] phosphorothioate (compound number 15) 4-(2,4-dichlorobenzoyl)-1-methyl-5
-Hydroxypyrazole 156 F (0,005 mol), triethylamine 0.51 F (0,005 mol), 0,0-diethylthiophosphoric acid chloride 0.949
After dissolving (0,005 mol) in 20 ml of benzene,
The mixture was heated under reflux for 5 hours while stirring.

After the reaction was completed, the same post-treatment and purification as in Example 5 were carried out,
The desired product was obtained as an oily substance, o, 53F.

(Yield 25cm) 'H-NMR (δ, ppm, 0DO4): 1j
5 (6H, t, J=7H2).

5.82 (3H,!9), 4.28 (4H,q,
d, J=7H2, :J=10H2).

739-750 (4H) Next, the compounds shown in Table 1 were synthesized in the same manner as in Examples 1-6. The compounds of the present invention obtained in Examples 2 to 6 are also shown in Table 1.

Oh.

Next, the following compounds can be easily synthesized according to the above examples. These are shown in Table 2.

However, the compounds of the present invention are not limited to these.

Table 2 Next, 9 When applying the compound of the present invention as a herbicide, a suitable carrier 1, such as a solid carrier such as clay, talc, bentonite, or diatom, or water, alcohols (methanol, ethanol, etc.), aromatic Group hydrocarbons (
benzene.

toluene, xylene, etc.), chlorinated hydrocarbons.

Ethers, ketones, esters (ethyl acetate, etc.),
It can be applied in combination with a liquid carrier such as acid amides (dimethylformamide, etc.).

Emulsifiers, dispersants, suspending agents, penetrating agents, if desired.

Adds spreading agents, stabilizers, etc., emulsions, and hydrating agents.

It can be put to practical use in any dosage form such as a powder or 0 granules.

In addition, when spraying the formulation or fct- as necessary, use other herbicides, various insecticides, fungicides, planting preparations, synergists, etc.
ook” 69th eye of public
ation (19B 5) There are compounds described in IC.

Formulation Example 1 Emulsion Invention Compound A10 ・・・・・・・・・・・・・・・
・・・ 60 copies ・・・・・・・・・・・・
・・・・・・・・・ 45 part crane hole 2680 ・・・
・・・・・・・・・・・・・・・ 10f! I.

(Toho Chemical C1!l product name) Dimethylformamide ・・・・・・・・・・・・・・・・・・
... 15g11 or more are uniformly mixed to form an emulsion. When spraying, dilute the entire emulsion with an appropriate amount of water and spray.

L anal breast reduction Compound A of the present invention 15 ・・・・・・・・・・・・・・・
...20 copies...
, , , , , , 7 5 parts Tsurupol 2680 ・
・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・ 5 parts (surfactant; fluorinated Pfi(1) trade name) or more are uniformly mixed to form an emulsion. When using, mix the above emulsion with water to 50 to 1
．． It is diluted 1,000 times and sprayed at an effective amount of 5 to 1,000 tons per 10 are.

Formulation example 5 Wettable powder Compound of the present invention A I 1 ・・・・・・・・・・・・・
・・・・・・ 50 parts Sieglite A ・・・・・・・・・
・・・・・・・・・・・・ 46 parts (Kaolin clay: Sieglite Industries ■Product name) Tsurupol 5059 ・・・
・・・・・・・・・・・・・・・ 2 parts (mixture of nonionic surfactant and anionic surfactant; Toho Kado brand name) Carplex (anti-caking agent)・・・・・・・・・
...... Two or more parts (white carbon; Shionogi [Yakuzai 0 brand name)] or more are mixed and ground uniformly to make a wettable powder.

Series of enrichment "1" - Hydrating agent Compound of the present invention A15 ・・・・・・・・・・・・・・・
・・50 parts Sieglite A ・・・・・・・・・・・・
・ 46 parts (kaolin clay; Zikrite Industries (public product name) Tsurupol 5059 ・・・・・・・・・・・・
・・・・・・ 2 parts (mixture of nonionic surfactant and anionic surfactant; Toho Kado brand name) Carplex (anti-caking agent) ・・・・・・・・・・・・
・・・・・・ Two or more parts (white carbon: Shionogi & Co., Ltd. proprietary product name) are uniformly mixed and pulverized to make a wettable powder.

- Layout L row” - Flowable compound door of the present invention 20 ・・・・・・・・・・・・・・・
・25 parts Ageli Seal 8-710 ・・・・・・・・・
......10 parts (nonionic surfactant: Kao Atlas ((υ brand name) Lunox 1oooa...
・・・・・・・・・・・・・・・・05 parts (anionic surfactant; Toho Chemical ■trade name) 1 Tyrodobol water
・・・・・・・・・・・・・・・・・・20 parts (thickener: Lone Boulin product name) Water ・・・・・・・・・
・・・・・・・・・・・・ 445 parts or more are mixed uniformly to form a flowable agent.

Formulation Example 6 Flowable Invention Compound Point 19・・・・・・・・・・・・・・・
... 25 copies Ageli Seal 8-710. ,,,,,,
, , , , , -, , 10 parts (nonionic surfactant; Kao Atlas ■ trade name) Lunonox 1oooc ・・
・・・・・・・・・・・・・・・・・・ 05 parts (anionic surfactant; for Toho Chemical) Trade name) 1 Tyrodobol water ・・・・・・・・・・・・・・・・・・ 20 parts (thickener; Lone Boulin product name) Water ・・・・・・・・・
・・・・・・・・・・・・ 44.5 parts or more are mixed uniformly to form a flowable agent.

Formulation example 7 Grains: Compound A of the present invention; 24 ・・・・・・・・・・・・・・・
・・・・・・・・・ 5th part bentonite ・・・・・・・・・
・・・・・・・・・ 55th part ri ・・・・・・
・・・・・・・・・・・・・・・ More than 40 parts were uniformly mixed and pulverized, mixed with a small amount of water, stirred and kneaded, and granulated using an extrusion type granulator.

Dry and make into granules.

In addition, the compound of the present invention can be used in appropriate amounts for controlling various weeds in farmland such as playgrounds, vacant lots, and railway edges, in addition to agricultural and horticultural fields such as fields, paddy fields, and fruit orchards, and the amount of application is applicable. Scene, use) old period.

Although there are differences depending on the application method, target grass species, cultivated crops, etc.
Generally per hectare + ha).

A ratio of about 2 to 0.0025 to 10 is appropriate.

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

Test fl11 Weeding effect test by soil destruction treatment Opening area i/100 Oa, depth 10 holes.

Put a sterilized diluvial soil tank into a plastic bot.

Japanese wild grass, Japanese fir tree, Japanese grasshopper, Japanese knotweed, and Japanese blackberry were each sown in spots, and after covering the soil with about 15 layers of soil, the amount of the active ingredient was uniformly spread over the broken soil surface at a predetermined ratio.

The chemical solution used for spraying was as follows: the above-mentioned formula J and emulsion were diluted with water and sprayed 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 criteria below. The results are shown in Table 3.

Judgment Criterion 5: Weed killing rate of 90% or more (almost complete death) 4...
・Weed killing rate 70-90% 6...Weed killing rate 40-70 inches 2...Weed killing rate 20-40 inches...Weed killing rate 5-20 percent 0...Weed killing rate 5 inches or less (mostly effective) None) However,
The above-mentioned weed killing rate was determined by measuring the above-ground grass weight in the chemically treated area and the above-ground fresh grass weight in the non-treated area using the following formula 2.τ.

Table 6 Test Example 2 Phytotoxicity test on cultivated plants by soil destruction treatment Vertical 15-1. Put the sterilized dolphin grass into a plastic box with width of 22 bunches and depth of 6 cm, sow corn and trumpet gum, and cover the soil with about 15 m of soil, then spread it evenly over the soil surface so that the amount of active ingredients is at the specified ratio. was dispersed. The chemical solution used for spraying was the water concentrator or emulsion of the formulation example described above diluted with water and sprayed over the entire surface with a small sprayer. Five weeks after the chemical spraying, the crops were investigated for chemical damage according to the following criteria. The results are shown in Table 4.

Judgment Criteria 5...Almost complete death of crops 4... 〃 Significant phytotoxicity 5... 〃 I Phytotoxicity is observed 2... l I Slight phytotoxicity is observed 1... 〃
〃 Almost no phytotoxicity observed 0... No phytotoxicity observed on crops Table 4 Test Example 3 Herbicidal effect test under flooded conditions (1) 1/1
After placing the alluvial soil in a Neubauerbott of 0,000 are, water was added and mixed to create a water-filled condition of 2 centimeters of water. Tainubier, Konagi.

Seeds of Azena, Kikashigusa, and Firefly were mixedly sown in the pots mentioned above, and the beds were placed (Niurikawa tubers, Mizugaya Tsurugi tubers, and Kurogwai tubers ff1k).The next day, the drug diluted solution was poured onto the water surface at a predetermined dose. was added dropwise with a graduated pipette.

Six weeks after dropping the chemical solution, the herbicidal effect on various weeds was investigated according to the following criteria.

The results are shown in Table 5.

Criterion 5: Weed killing rate of 90 inches or more (almost complete death) 4...
・z 70 ~ 90 Chi 5... # 40 ~ 70% 2... 1 20 ~ 40 Chi 1... # 5 ~ 20 Chi 0... # 5% or less (almost no effect) However The above weed killing rate 1-t' was determined by the following formula by measuring the above-ground weeding in the chemical-treated area and the above-ground weeding in the untreated area.

Table 5 - Test 1 No. Weeding effect test under flooded conditions @ (2)
115. After placing an alluvial soil moat in a Hugner pot, water was added and mixed to create a water depth of 2.

Cyperus clump violet and Kurogai clump violet collected from a paddy field with a lot of perennial weeds in the previous year were planted in the soil destruction of Wagner Bonoto under the above-mentioned flooding conditions, and firefly seeds were scattered in rapid succession.

Immediately after the weeds germinated, a diluted drug solution was dropped onto the water surface using a volumetric pipette so as to achieve a predetermined dose VC. Six weeks after dropping the chemical solution, the fresh weight of various weeds was measured, and the herbicide rate was calculated. However, the whitened parts of the weeds were counted as dead parts and are shown in Table 6.

Table 6 Structural formula 11 of the control compound used in Test Examples 1 to 4 is as follows.

Alachlor: Patent Applicant Nissan Chemical Industries, Ltd. Procedural Correction @ (Method) December 1980 jJ IEI Commissioner of the Patent Office Kazuo Wakasugi 1 Indication of Case 1981 1) Patent Application No. 158859 2 Invention Name Pyrazole Derivatives and Selective Herbicides 3 Relationship with the Amendment Case Patent No. 81 Applicant Address 3-7-14 Kanda Nishiki-cho, Chiyoda-ku, Tokyo 101
? November 29, 1982 (Shipping date) 5? iiii Positive full text before target details 6? ili positive content

Claims (1)

[Claims] (1) General formula (■): OH. (In the formula, or represents a halogen atom or a nitro group, yH
Indicates a hydrogen atom, lower alkyl group or halogen atom,
z#'i represents a methanesulfonyl group spanning a halogen atom. ) or its organic acid ester. OH3 (in the formula, or represents a halogen atom or a nitro group, Y represents a hydrogen atom, a lower alkyl group or a halogen atom,
Ztlj)・Represents a rogen atom or a methanesulfonyl group. ) or an organic acid ester thereof as an active ingredient.