JPS5931775A - Pyrazolesulfonylurea derivative, its preparation and herbicide containing said derivative - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [A is H, alkyl or phenyl; B is H, alkyl, alkoxy, aralkyl, etc.; C is H, alkyl, halogen, phenyl, etc.; X is H, alkyl, alkoxy, or halogen; Y is H, alkyl, alkoxy, CF3, halogen, alkylamino, etc.; Z is N or CR12 (R12 is H, halogenated alkyl, etc.)]. EXAMPLE:N-[(4-Methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-1,3-dimeth yl-5- methoxypyrazole-4-sulfonamide. USE:Herbicide having high herbicidal activity at low rate of application. PROCESS:The compound of formula I can be prepared by reacting the pyrazole- sulfonylisocyanate derivative of formula II with the aminopyrimidine or aminotriazine derivative of formula III in an inert solvent.

Description

[Detailed description of the invention] The present invention is.

(1) General formula (I); [In the formula, A represents a hydrogen atom, a lower alkyl group, or a phenyl group, and B represents a hydrogen atom, a lower alkyl group, an aralkyl group, or a lower alkoxy group.

halogenated alkyl group, 00. R(Rid hydrogen atom.

Lower alkyl group, -OH, 0H=OH, or -O
H, Omi OH)・ao N<'°(R+
is a hydrogen atom, lower R.

It represents an alkyl group or a phenyl group, and R3 represents a hydrogen atom or a lower alkyl group.

), 5(0)nFt, (R represents a lower alkyl group and n represents an integer of 0.1.2) or a phenyl group which may be substituted with a lower alkyl group, a halogen atom, or a nitro group represents.

C is a hydrogen atom, a lower alkyl group, an aralkyl group + a lower alkyl group/N, co, R.

(R4 is a hydrogen atom, a lower alkyl group, -oH, ar
−+=cH.

Or -OH,0! O) (represents), OON/'
・(Fl, is \R.

Represents a hydrogen atom, lower alkyl group or phenyl group +
Ra represents a hydrogen atom or a lower alkyl group. )
, 5(0)rJ, (RF represents a lower alkyl group, n represents an integer of 0.1.2), and R represents a lower alkyl group.

) or a phenyl group which may be substituted with a lower alkyl group, a rogen atom, or a nitro group. X is a hydrogen atom,
It represents a lower alkyl group, a lower alkoxy group, or a fcFi/.logen atom, and Y is a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower alkoxyalkyl Al0FI.

Each represents a hydrogen atom or a lower alkyl group. ),
represents an alkylamino group or a dialkylamino group,
2 is an N atom or 2C-R+t (RI! is a hydrogen atom,
- May form a 5-membered ring structure containing an oxygen atom together with the logogenated alkyl group or UY. ). ] The present invention relates to a novel pyrazolesulfonylurea derivative represented by the following, a method for producing the same, and a herbicide containing the derivative as an active ingredient.

The compound of the present invention is a new compound that has not been described in any literature and has excellent physiological activity as a herbicide.

Japanese Patent Publication No. 55-102577 and Japanese Patent Publication No. 159-1983
Publication No. 466 describes that pyridine sulfonylurea derivatives are useful as herbicides and 12 as pyridine sulfonylurea derivatives.

Conventionally, it has been generally accepted that the economic cost of using herbicides depends on the amount of active ingredient treated per unit area.
The search for compounds that exhibit high herbicidal effects at low doses has been carried out for many years.

Many compounds are conventionally known as pyrazole derivatives.
No. 41872, JP-A-57-2276, JP-A-57-
No. 58670 and Japanese Unexamined Patent Publication No. 51-135265 are known.

As a result of many years of research, the present inventors have discovered that the compound of the present invention has significantly higher herbicidal efficacy than the previously known pyrazole derivatives mentioned above, and is therefore practically useful. On the other hand, as sulfonylurea derivatives containing a nitrogen-containing heterocycle, the above-mentioned virolsulfonylurea and pyridine sulfonylurea are known, but the compound of the present invention has a significantly higher herbicidal effect compared to these known compounds. The present invention was completed based on the following findings.

In other words, the compounds of the present invention can significantly reduce the amount of active ingredients applied per unit area compared to these conventionally known compounds, have extremely large economic effects compared to conventional herbicides, and can also reduce the amount of pesticides used. It can be said to be a revolutionary herbicide that can significantly reduce the risk of environmental pollution when applied.

Examples of compounds in which the derivative represented by the general formula (1) is used as a herbicide are shown in Table 1 below.

However, compound boiling is referred to in the following description.

Table 1 13- The compound of the present invention is represented by the general formula (1).

It can be easily produced using the following reaction formula.

Reaction formula l [wherein A, B, C, X, Y and 2 represent the same meanings as above. ] By bathing the pyrazole sulfonyl isocyanate derivative (old) in a sufficiently dried inert solvent such as dioxane or acetonitrile, and adding pyrimidine or triazine derivative (Ill) to the mixture and stirring. ,
Generally, the compound (+) of the present invention can be obtained by rapidly reacting. If the reaction is difficult to proceed, the reaction can be easily proceeded by adding a small amount of a suitable base such as triethylamine, triethylenediamine, pyridine, sodium ethoxide, or sodium hydride.

59- The raw material pyrazole sulfonyl isocyanate is used in U.S. Pat.
Pyrarazole sulfonamide can be synthesized with reference to Japanese Patent No. 210, and pyrarazolesulfonyl isocyanate can be further synthesized with reference to the method described in Japanese Patent Publication No. 55-13266M.

-61=60- Reaction formula 2 That is, pyrazole sulfonamide derivative (lV')
is reacted with an alkyl chlorocarbonate in a solvent such as acetone or methyl ethyl ketone in the presence of a base such as potassium carbonate, and after one reaction, the compound (V) is precipitated with hydrochloric acid or the like to obtain compound (V). The compound (1) of the present invention can also be prepared by heating the compound (lIl) in a solvent such as toluene.

Furthermore, the compound (1) of the present invention can be obtained more easily by synthesizing R=c, H, in compound (V) with reference to JP-A-57-56452 and carrying out the reaction in the same manner as above. can.

62 - Reaction equation 3 (1v) control)
(1) Referring to JP-A-56-154471, pyrazole sulfonylamide derivative (IV') and pyrimidine tfiJ: triazine isocyanate (V
J),! : Compound (Vll) can be synthesized by a reaction, and the compound (1) of the present invention can also be synthesized by secondarily reacting it with sodium alcoholade.

Aminopyrimidine, on the other hand, is known as The Chemistry of
Heterozyclink Compounder (Interxience Haflishers Inc. New York) ['I'be Chemistry of
Heter-ocyclic compounds (
IntOrscience ) publishers I
It can be synthesized with reference to The Pyrimidines, Vol.

I cut it. Aminotriazines are listed in the Journal of Organic Chemistry (Ir.
Ganic Ohem-istry) Volume 28, 181
It can be synthesized by the method described on pages 2-1821 (1963).

2-AεNo 4-Menalu 5.6-Sihydrofuro [2,
3-cl]pyrimidine and 2-amino-4-chloro-5β-chloroethyl-6-methylpyrimidine in the Journal of Organics.

It can be synthesized by the method described in Chemistry Vol. 16, p. 1153 (1951).

Most of the intermediates used in this invention.

This is a new compound, and an example of its synthesis is shown below as an example.

Reference Example 1 Synthesis of 1.3-dimethyl-5-methoxypyrazole-4-sulfonamide Add 1,3 to 70 mt of chlorosulfonic acid at 5°C or lower with cooling.
-dimethyl-5-methoxypyrazole 12,67 (0
, 1 mol) was added dropwise. After the addition, the mixture was heated and stirred at 100° C. for 8 hours. After that, it was cooled to 0°C, and 11.9'r of thionyl chloride (0,1
mol) was added dropwise over 60 minutes. 2 at 100℃ after dropping
The mixture was heated and stirred for hours. The reaction mixture was ice-cooled and carefully poured into ice water to yield crude 1,3-dimethyl-5-methoxy-pyrazole-4-sulfonyl chloride I:I as crystals.

The crystal 1' was separated, dissolved in 2.0 g of tetrahydrofuran, and added dropwise to aqueous ammonia at 10°C or lower.

After the addition, the mixture was stirred at room temperature for 60 minutes. When low-boiling components were distilled off from the reaction mixture under reduced pressure, crystals were precipitated.

When the crystals are separated, washed with water, and dried, 1, with a melting point of 144-6℃ is obtained.
11.5 f of 3-dimethyl-5-methoxy-pyrazole-4-sulfonamide was obtained.

Reference Ga 2 Synthesis of 1.5-dimethyl-3-trifluoromethyl-pyrazole-4-sulfonamide Ethanol bath solution of trifluoroacetylacetone 25y (0.16 mol) 100#+7! Methylhydrazine 7,4 at 15℃ or below 65-? (0.16 mol)
was dripped. After stirring at room temperature for 3 hours and overnight, the solvent was distilled off to obtain 192v of 1,5-dimethyl-3-trifluoromethylpyrazole as an oil. Following Reference Example 1, 1,5-dimethyl-3-trifluoromethylpyrazole-4-sulfonyl chloride 2qy'c was obtained by reacting with chlorosulfonic acid and thionyl chloride, and by reacting with aqueous ammonia in tetrahydrofuran solvent, a melting point of 204 1,5-dimethyl- at ~206°C
21.5 units of 3-trifluoromethylpyrazole-4-sulfonamide were obtained.

Reference Example 3 Synthesis of 1,3-dimethyl-5-methoxycarnylpyrazole-4-sulfonamide Add 200 g of ethyl 1,3-dimethyl-5-pyrazolecarboxylate to 200 g of chlorosulfonic acid at 5° C. or lower with cooling, 4 F (αs, 1o1
) was added dropwise.

After heating and stirring at 120°C for 10 hours, the mixture was poured into ice water.

Extracted with ether. Wash with water, dry and remove temporary solvent = 66
- Crude 1,3-dimethyl-4-chlorosulfonyl-5-pyrazolecarboxylic acid 497 was obtained as a solid.

Take 2 h 9 Y (0,1+nol) and dissolve it in 60 d of tetrahydrofuran VC @ 7 mm = 7 water 150 t
IltEPK was added dropwise at a temperature below 10°C.

The mixture was stirred at room temperature for 4 hours and concentrated to dryness under reduced pressure.

Next, 300 grams of dry methanol was added, and the mixture was heated under reflux for 3 hours while passing hydrogen chloride gas. After the reaction, methanol was distilled off, ice water was added, and the mixture was extracted with ethyl acetate. Washing with water, ifj, and ice testing After distilling off the solvent and recrystallizing the obtained crude crystals from methanol, 1,3-dimethyl-5-
Methoxycarbonylpyrazole-4-sulfonamide 9
．． 02 was obtained.

Reference Example 4 Synthesis of 1.3-dimethyl-5-n-propylsulfonylpyrazole-4-sulfonamide 1,6-dimethyl-5-chlorpyrazole was prepared according to the above reference example using 1.3-dimethyl-5-chlorpyrazole as a raw material. A -4-sulfonamide melting point of 173°C was obtained. The above sulfonamide 141y ([L067mol), sodium hydroxide 107y (0,268mol) and D
n-propyl mercaptan 6 in a mixture of MF 120-
6t (0,087 mol) was added dropwise at room temperature.

After dropping, it was heated at 80 to 90°C for 3 hours.

After the reaction was completed, DMF was distilled off under reduced pressure, water was added, and the mixture was diluted with concentrated hydrochloric acid.
i (4), and the precipitated crystals were collected in a furnace.

1,6-dimethyl-5- with a melting point of 105-106°C after drying
n-7'pylthiovirazole-4-sulfonamide 1
4.5 F was obtained.

Next, this intermediate is acetic acid 80#+7! The solution was dissolved in a bath, and 251 liters of 30X hydrogen peroxide solution was added dropwise to the solution while cooling with water.

After stirring at room temperature for 4 hours, the mixture was poured into water.

By collecting the precipitated crystals, 1,6-dimethyl-5-n-propylsulfonylpyrazole-4-r sulfonamide having a melting point of 127 to 129°C was obtained.

The following substituted pyrazole sulfonamides (■) were synthesized according to the general method described in Reference Examples 1 to 4.

Reference Example 5 Synthesis of 1.5-dimethyl-3-phenylpyrazole-4-sulfonamide It was obtained from 1°5-dimethyl-3-phenylpyrazole according to the above-mentioned Reference Example.

Melting point 144-148°C Reference Example 6 Synthesis of 1-methyl-5-chlorpyrazole-4-sulfonamide Obtained from 1-methyl-5-chlorpyrazole.

Melting point: 159-162°C Reference Example 7 Synthesis of 1,5-dimethyl-3-methoxycarbonylvirazole-4-sulfonamide Obtained from 1,5-dimethyl-3-methoxycarbonylpyrazole.

Melting point: 183-185°C Reference Example 8 Synthesis of 1,5-dimethyl-6-nitoxycarbonylvirazole-4-sulfonamide Obtained from 1,5-dimethyl-3-ethoxycarbonylpyrazole.

Melting point: 159-161°C Reference Example 9 Synthesis of 1,5-dimethylpyrazole-4-sulfonamide Obtained from 1,3-dimethylpyrazole.

Melting point: 114-115℃ Reference example 10 Synthesis of 5-dimethylpyrazole-4-sulfonamide , 5.5-dimethylpyrazole.

Melting point: 215-226°C Reference Example 11' Synthesis of 1,5-dimethylpyrazole-4-sulfonamide Obtained from 1,5-dimethylpyrazole.

Melting point: 165-166°C Reference Example 12 Synthesis of 1-methyl-3-1-propyl-5-methoxypyrazole-4-sulfonamide Obtained from 1-methyl-3-1-propyl-5-methoxypyrazole.

Melting point: 114-115°C November 1911: 1.3-cymey-5-ethoxycarbonylpyrazole-4-sulfonamitono synthesis 1. Obtained from s-dimethyl-5-ethoxycarbonylpyrazole.

Melting point j50-154°C Reference example 14 1-phenyl-! i, Synthesis of 5-dimethylpyrazole-4-sulfonamide Obtained from 1-phenik-3,5-dimethylpyrazole.

Melting point 178~IEIO℃ Substituted pyrazole sulfonamide GV obtained in reference example)
A specific example of synthesis of two compounds of the present invention will be explained using the following.

However, it is not limited to these only.

Example I Synthesis of N-((4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-1,3-dimethyl-5-methoxypyrazole-4-sulfonamide (Compound A292) Obtained in Reference Example 1 The sulfonamide 10.25y (ao
smol), dry potassium carbonate &292 (0,06mol
1), 4.95 t (0.05 m01) of n-butyl isocyanate was added to a mixture of 50 g of dry acetone at room temperature and stirred for 4 hours.

Then, the mixture was heated to reflux for 1 hour. After the reaction, acetone was distilled off under reduced pressure, and the residue was dissolved in 200 mε water. After separating a trace amount of water-insoluble materials, the P solution was precipitated with hydrochloric acid, and the resulting crystals were separated from P and washed with water.

Upon drying, 92V of N-(butylcarbamoyl)-1,S-dimethyl-5-methoxy-pyrazole-4-sulfonamide with a melting point of 135-142°C was obtained.

100 J of dry benzene and N-(butylcarbamoyl)-1,3-dimethyl-5-methoxy-pyrazole-4-sulfonamide 9,12 f (0,0
5 mol') of phosgene a9 under heating under reflux.
f/ (0.09 mol) was bubbled in over 1.5 hours; f: was followed by heating under reflux for 30 minutes.

After the reaction is complete, benzene is distilled off under reduced pressure to obtain an oily crude 1,5
-dimethyl-5-methoxy-pyrazole-4-sulfonylisocyanate was obtained.

This crude incyanato 1.599 (0,006 mol
) fc was taken out and soaked in 20-dry acetonitrile K bath, 0.695 y of 4-methoxy-6-methyl-2-aminopyrimidine (α005mob) was added thereto, and after stirring at room temperature for 1 hour, the mixture was heated to reflux. After 30 minutes, it was cooled.

By separating the formed crystals, washing and drying, the melting point is 1.
1.091 of N-((4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-1,3-dimethyl-5-methoxy-pyrazole-4-sulfonamide was obtained at 83-4°C.

Example 2 Synthesis of N-((4-methoxy-6-methyltriazin-2-yl)aminocarbonyl]-1,6-dimethyl-5-methoxycarbonylpyrazole-4-sulfonamide (Compound 4387) Obtained in Reference Example 3 N-(,-butylcarbamoyl) was prepared according to the method of Example 1 using the obtained sulfonamide 6.81.
-1,3-dimethyl-5-methoxycarbonylpyrazole-4-sulponamide a b y (o, 02 I
s mol) was obtained. The obtained compound was mixed with xylene 20
The mixture was mixed with 0.05 g of phosphatide and 77y (0,078@J) of phosphorus was blown into the mixture under reflux for 1.5 hours. After heating under reflux for 30 minutes, xylene was distilled off to obtain oily crude 1,3-dimethyl-5-methoxycarbonylpyrazole-4-sulfonylisocyanate.

This crude insyanur) [190F (0,0055m
ol)'(r taken out, dissolved in 20,7 liters of dry acetonitrile, and added 4-methoxy-6-methyl-2-aminotriazine (0,00251 units)
After adding ol)f and stirring at room temperature for 2 hours, the mixture was heated under reflux for 60 minutes and cooled [7]. Separately wash the crystals formed from 1 to 1 using P.

When dried, N-[(4
11 compounds of -1,3-dimenal-5-methoxycarbonylpyrazole-4-sulfonamide were obtained.

Next, according to the above examples, the specifically synthesized compounds were compared to the compounds synthesized in Examples 1 and 2 (compound, %292,
387) and are shown in Table 2 below.

Table 2: In order to apply the compound of the present invention as a total herbicide, a suitable carrier 2, for example, a solid carrier such as clay, Merck, bentonite, diatomaceous earth, etc., or (c) water, alcohols (methanol, ethanol, etc.), aromatic group hydrocarbons (benzene, toluene, xylene, etc.), chlorinated hydrocarbons, ethers, ketones, esters (ethyl acetate, etc.).

It can be applied by mixing it with a liquid carrier such as acidamides (dimenalformamide, etc.) 2. If desired, an emulsifier 1. A dispersing agent, suspending agent, penetrating agent, spreading agent, stabilizer, etc. can be added.
Liquids, emulsions, irrigation agents.

It can be put to practical use in any desired dosage form, such as a two-grain powder.

Next, examples of formulations of herbicides containing the compound 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, "parts" mean parts by weight.

Formulation example] Wettable powder Compound A2 of the present invention
・・・・・・・・・・・・・・・ Part 5 Sieglite A
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・ 46 parts (Kaolin thread relay: Sieglite Industries ■Product name) Tsurupol 5039 −
−−−−2 Arms (Mixture of nonionic surfactant and anionic surfactant: Toho Chemical ■Product name) Carplex (anticaking agent) −−−−−z
'Q (White Carbon: Shionogi & Co., Ltd.'s product name) and above are mixed and crushed uniformly to make an irrigation agent. When using
Add hydration powder to 50-50% with water. Dilute it to 0 times and spray it so that the amount of active ingredient is 0,000 kg to 10 kg per hectare.

Formulation example 2 Wettable powder Compound of the present invention 86 ・・・・・・・・・・・・・・・
・・・・・・・・・ Part 75 Sieglite A...
・・・・・・・・・・・・・・・・・・・・・ 19
Part (Kaolin thread relay: Sieglite Industries ■Product name) Tsurupol 5039 ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・ 2 parts (Mixture of nonionic surfactant and anionic surfactant 2 Toho Chemical ■Product name) Carplex (anti-caking agent)・・・・・・・・・・・・
...4 parts (white carbon: Shionogi & Co., Ltd. ■trade name) or more are mixed and ground uniformly to make an irrigation agent.

81- Formulation example 3 Hydrating agent Inventive hardware shop 140...
・・・・・・ 50 parts Sieglite A ・・・・・・
・・・・・・・・・・・・・・・・・・・46 parts (Kaolin clay: Sieglite Industries ■Product name) Tsurupol 5059 ・・・・・・・・・・・・・・・...
・・・ 2 parts (Mixture of nonionic surfactant and anionic surfactant: Toho Chemical ■Product name) Carplex (anti-caking agent)・・・・・・・・・・・・
Two or more parts (White Carbon: Shionogi Co., Ltd. flavored product name) are mixed and pulverized uniformly to make an irrigation agent.

Distribution example 4 Hydrating agent Inventive hardware shop 159・・・・・・・・・・・・・・・
・・・・・・・・・ 50 parts Sieglite A ・・・
・・・・・・・・・－・・・・・・・・・・・・・・・・・・
・ 46 parts (kaolin clay; Sieglite Industries ■Product name) Tsurupol 5039 ・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・ 2 parts (Mixture of nonionic surfactant and anionic surfactant: Toho Chemical ■Product name) Carplex (anti-caking agent)・・・・・・・・・・・・
・ Part 2 (White Carbon: Shionogi & Co., Ltd. ■Product name)
The above is uniformly mixed and pulverized 2 to make an irrigation agent.

82- Formulation example 5 Wettable powder Compound of the present invention 292・・・・・・・・・・・・・・・
・・・・・・ Part 25 Sieglite A ・・・−・・・
・・・・・・・・・・・・・・・・・・・・・ 71 copies (
Kaolin clay: Sieglite Kogyo ■Product name) Tsurupol 503?・・・・・・・・・・・・・・・・・・
・・・・・・・・・ 2 parts (Mixture of nonionic surfactant and anionic surfactant: Toho Chemical ■Product name) Carplex (anti-caking agent)・・・・・・・・・...
・ Part 2 (White Carbon: Shionogi & Co., Ltd. ■Product name)
The above is uniformly mixed and pulverized to form a wettable powder.

Formulation example 6 Wettable powder Compound of the present invention &384・・・・・・・・・・・・・・・
・・・・・・ 50 parts Sieglite A ・・・・・・
・・・・・・・・・・・・・・・・・・・・・ 44 parts (Kaolin clay: Sieglite Industries ■Product name) Sowa Ball 5o59・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・ 4 parts (Mixture of nonionic surfactant and anionic surfactant: Toho Chemical ■Product name) Carplex (anti-caking agent)・・・・・・・・・...
・ Part 2 (white carbon: Shionogi chestnut product name)
The above is uniformly mixed and pulverized to make an irrigation agent.

Formulation example 7 Hydrating agent Inventive hardware shop 387・・・・・・・・・・・・・・・
・・・・・・ Part 45 Sieglite A ・・・・・・
・・・・・・・・・・・・・・・・・・・・・ 51 parts (Kaolin clay: Sieglite Industries ■Product name) 7
Luhole 5039...Track/4...Track/
Part 2 (Mixture of nonionic surfactant and anionic surfactant 2 Toho Chemical ■Product name) Carplex (anti-caking agent)・・・・・・・・・・・・
... 2 states (white carbon: Shionogi Co., Ltd. flavor product name) or more are uniformly mixed and ground to make a wettable powder.

Formulation Example Day Emulsion Invention Compound A387・・・・・・・・・・・・・・・・・・
・・・・・・・・・ 2nd part
゛°゛゛°°°゛°Pa°°°°°°°゛°゛°”゛ 78 parts dimethylformamide
−−−−−−−−°°15 part vine pole 268o −・
・・・・・・・・・・・・・・・・・・・・・・・・
... 5 parts (mixture of nonionic surfactant and anionic surfactant: Toho Chemical ■trade name) The above is mixed uniformly to form an emulsion. In use, the emulsion is diluted 10 to 10,000 times with water and applied in an amount of 1005 to 10 kg of active ingredient per hectare.

Formulation Example 9 Flowable Invention Compound A 587 ・・・・・・・・・・・・
・・・・・・・・・ 25 parts Grisol S-710・
・－・・・・・・・・・・・・・・・・・・ 10 copies (
Nonionic surfactant: Kao Atlas ■Product name) Lunox 1oooa ・・・・・・・・・・・・・・・・・・
・・・・ α5 part (Anionic surfactant: Toho Chemical ■Product name) 1X Rhodobol water ・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・ 20 parts (thickener:
Lone Boulin product name) Water
・・・・・・・・・・・・－・・・・・・・・・・・・
... 44.5 parts or more are mixed uniformly to form a flowable agent.

In addition, the compounds of the present invention may be used as other herbicides, various insecticides, and fungicides when formulated or sprayed as necessary.

It may also be used in combination with a synergist.

Other types of herbicides mentioned above include 1, for example, Farm Chemicals Handbook (Farm Chemicals Handbook).
handtnnk) 68th edition (1982).

Note that the compound of the present invention can be applied to control various weeds in non-agricultural fields such as playgrounds, vacant lots, and railway edges, in addition to certain agricultural fields such as fields, paddy fields, and orchards, and the amount of application depends on the application situation. There are differences depending on the application time, application method, target grass species, cultivated crops, etc., but in general, the appropriate amount of active ingredient is about 0.05 to 10 Yu per hectare.

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

Test Example 1 Weeding effect test by soil treatment Vertical 15. , horizontal 2
Sterilized diluvial soil was placed in a 2 crn, 6 m deep plastic box, and rice, wild grass, crabgrass, cyperus,
Mixed sowing of Koakaza, Sperhyu, ... Kidamegiku, and Japanese doggrass.

After about 1.5 parts M of soil was added, the active ingredient was evenly spread over the soil surface so that the amount of the active ingredient was at a predetermined ratio.

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

The results are shown in Table 3.

Judgment Criteria 5: Weed killing rate 90X or higher (almost complete death) 4...
・Weed killing rate 5470-90% 3...Weed killing rate 40-70% 2...Weed killing rate 20-40X 1...Killing rate 5-20X Mouth...Weed killing rate 5X or less (hatondo) (no effect) However,
The above-mentioned weed killing rate was determined by the following formula by measuring the weight of above-ground plants in the chemically treated area and the weight of above-ground plants in the non-treated area.

87- Table 3 88- The ~black compounds in Table 3 above are as follows.

8 Control compound A (described in JP-A No. 56-169688) * Control compound B (described in JP-A-56-1696B8) * Control compound C (described in % open/closed publication No. 56-169688) 91- Test example 2 Yellow leaves Test of herbicidal effect by treatment Sterilized diluvial soil was placed in a plastic box measuring 1 StM in length, 22 cm in width, and 6 cm in depth, and rice, crabgrass, cyperus, cyperus, and leafminer.

Dog mustard, corn, soybean, and wheat.

Seed each tomato and yuzu in spots.

It was piled up about 1.5m. When each ridge plant reached the 2- to 3-leaf stage, the active ingredient was uniformly sprayed onto the grass blades at a predetermined ratio.

The medicinal solution used for spraying was the irrigation agent of the formulation example described above, diluted with water, and sprayed over the entire surface of the grass of various weeds 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 4.

Some of the compounds of the present invention have selectivity for certain crops.

92-Table 4 8 control compounds in Table 3/4. B and D are the same as Test 9'l11 above.

Patent applicant: Nissan Chemical Industries, Ltd. - 95 completed - Continuation of page 1 39100 307100) 0 Inventors: Yoshihiro Iwasawa Inside the Nissan Chemical Industries, Ltd. Central Research Laboratory, 722-1 Tsuboi-cho, Funabashi City (□□□Inventor: Toshiaki Sato Inside the Nissan Chemical Industries, Ltd. Central Research Laboratory, 722-1, Tsuboi-cho, Funabashi City (C Inventor: Takashi Inokai, within the Nissan Chemical Industries, Ltd. Biochemistry Research Laboratory, 1470 Oaza Shiraoka, Shiraoka-cho, Minamisaitama-gun, Saitama Prefecture) (C inventor: Oguchi Seiden Saitama Prefecture South) 1470 Oaza Shiraoka, Shiraoka-machi, Saitama-gun, Nissan Chemical Industries, Ltd. Biological Chemistry Research Institute (Spontaneous) February 25, 1981 Indication of the case 1982 Patent Application No. 142069 2 Name of the invention Pyrazole sulfonylurea derivative, Herbicide 3 containing the manufacturing method and the derivative Relationship with the case of the person making the amendment Patent applicant address 3-7-14 Kanda Nishiki-cho, Chiyoda-ku, Tokyo Column for detailed explanation of the invention in the specification to be amended.

5. Contents of the amendment (1) The following shall be additionally inserted from the last line on page 59 of the description.

(2) The following is additionally inserted after the last line of page 71 of the specification.

"Synthesis of 5-chloro-1,3-dimethylpyrazole-4-sulfonamide for reference plate Obtained from 5-chloro-1,3-dimethylpyrazole. Melting point 173°C Reference 1-methylpyrazole-4-sulfonamide Synthesis of 1-methylpyrazole, melting point 173°C, 1 bottle, 3-dimethyl-5-i-propoquinecarbonylpyrazur-4-sulfonamide [1,3-dimethyl obtained in Reference Example 3 -5-carboxylpyrazole-4-sulfonamide
Month/: Heated in the presence of hydrogen chloride in a J-ring (1 cypress).

Melting point: 105-108°C-] (3) The following is additionally inserted below the last line of page 71 of the specification.

Procedural amendment (spontaneous) March 7, 1980 Director-General of the Patent Office Kazuo Wakasugi 1 Indication of the case 1982 Patent application @ 142069 2 Name of the invention Pyrazole sulfonylurea derivatives, their production process, and weed control containing the derivatives Agent 3? Relationship with the case of the person making the correction Patent applicant address: 3-7-14 Kanda Nishiki-cho, Chiyoda-ku, Tokyo Column for detailed explanation of the invention in the specification to be amended.

5. Contents of amendment (1) The following is added below the last line of Table 1 on page 59 of the specification.

" (2) Add the following to the last line of page 71 of the specification.

Synthesis of 5-chloro-1,3-dimethylpyrazole-4-sulfonamide Obtained from 5-chloro-1,5-dimethylpyrazole.
Melting point: 173°C Reference Example 16 Synthesis of 1-methylpyrazole-4-sulfonamide Obtained from 1-methylpyrazole.

Melting point 122-123°C] Synthesis of 1,5-dimethyl-5-1-propoxycarbonylvirazole-4-sulfonamide 1,3-dimethyl-5-carboxyl-pyrazole-4 obtained in Reference Example 5
-Sulfonamide was obtained by heating in 1-propyl alcohol in the presence of hydrogen chloride.

Melting point: 105-108°C Reference Example 18 Synthesis of 6-nitoxycarbonyl-1-methyl-5-phenylpyrazole-4-sulfonamide A solution of 75d of lorsulfonic acid and 15% of dry oo*rum was cooled to 0°C. , 3-ethoxycarbonyl-1-methyl-5-phenylpyrazole 11.5? ([10
A solution of 25 mol of dry chloroform was added dropwise. The mixture was then stirred at room temperature for 1 hour and then under reflux for 3 hours. After the reaction, chloroform was distilled off to obtain oily 3-ethoxycarbonyl-1-mef-5-7enylvirazole-4-sulfonic acid.

Next, add phosphorus pentachloride 2α91 little by little at room temperature,
The mixture was stirred at 100°C for 1 hour.

By adding to ice water and extracting with ether.

Oily 3-ethoxycarbonyl-1-)! f roux 5-7
Enylhyrasole-4-sulfonyl chloride 14.7
Fi Tokusou. Next, the obtained sulfonyl chloride was treated with acetone zogzVCgM'F, and KIT (io, 4.
48 t was added. Ammonia water (28X12.7F,
After dropping 76.5ml of solution at room temperature,
Heated at ℃ for 30 minutes. After distilling off the acetone, water was added to precipitate the target compound 12.9f as a solid.

Be/zen reunion a4p obtained. Melting point: 141-4°C.

Reference Example 19 Synthesis of 1-ethyl-5-methyl-6-methoxycarbonylpyrazole-4-sulfonamide Obtained from 1-ethyl-5-methyl-3-methoxycarbonylpyrazole.

Melting point: 165-168°C.

Reference Example 20 Synthesis of 1,5-dimethyl-5-dimethylcarbamoylpyrazole-4-sulfonamide Better than 1,3-dimethyl-5-dimethylcarbamoylpyrazole.

Melting point: 150-152°C.

Reference Example 21 Synthesis of 5-ethyl-1-methyl-3-methoxycarbonylpyrazole-4-sulfonamide Obtained from 5-ethyl-1-methyl-3-methoxycarbonylpyrazole.

Melting point: 188-191°C Reference Example 22 Synthesis of 1-ethyl-3-methyl-5-methoxycarbonylpyrazole-4-sulfonamide Obtained from 1-ethyl-3-methyl-5-methoxycarbonylpyrazole.

Melting point 130-133°C Reference Example 23 Synthesis of 3-ethyl-1-methyl-5-methoxycarbonylpyrazole-4-sulfo/amide Obtained from 6-ethyl-1-methyl-5-methoxycarbonylpyrazole.

Melting point 162-165°C Reference example 24 Synthesis of 1.3-dimethyl-5-(N,N-tetramethylenecarbamoyl)-4-sulfo/amide 1.3-dimethyl-5-IN,N-tetramethylenecarbamoyl)pyrazole I got more.

Melting point: 92-95°C.'' (3) Add the following between the 10th and 11th lines of the 75th line of Ming #i11 Homare.

[Example 3 N-[(4,6-dimetherbyrimidin-2-yl)aminocarbonyl]-1j-dimethyl-5-
Synthesis of propenyloxycarbonylvirazole-4-sulfonamide (compound layer 425) N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl)-1,3-dimethyl-5-methoxycarbonylpyrazole-4 -Sulfonamide (compound 43
841. Mu31(a00864motl'(r
17.411 tons of methanol.

10X sodium hydroxide F3.7? Add to the mixture of 4
Heat for 5 minutes 11[[,ta]. After the reaction, the mixture was acidified with concentrated hydrochloric acid to obtain a hydrolyzed compound (compound 4435) 2.3#'. The above compound 1.5 y (0,00408m
otlk was taken and added to THF8d, and triethylamine 0.4161f was added. After stirring for 10 minutes, no frills of bromide were added.
495F.

A THF a-solution was added, and the mixture was heated under reflux for 3 hours.

After a salt bath was removed, some of the THFi was distilled off to precipitate the target crystals a and sy.

Melting point 180-183°C Example 4 N-[(4,6-cymethoxy1,3.
5-triazin-2-yl)aminocarbonyl]-1,
5-dimethyl-5-dimethylcarbamoylpyrazole-
Synthesis of 4-sulfonamide (compound layer 484) 15 ml of dry acetonitrile. Inside, sulfonamide t97y obtained in Reference Example 21 (0,008 mot1.
Dichloro-8-triazinyl isocyanate 1.68
f (0,0088 mot) was added, and the mixture was heated under reflux for 1 hour. When left at room temperature, crystals of N-[(4,6-dichloro-1,3,5-triazin-2-yl)aminocarbonyl]-1,3-dimethyl-5-dimethylcarbamoylpyrazole-4-sulfonamide 2.2V was obtained. Melting point 182-185°C.

Next, the compound 1.31 (0,00297 motl
and added it to methanol 12d. Sodium methoxide obtained from 11.205 t of metallic sodium and 5 d of methanol was added little by little at room temperature. When the heat generation stopped, methanol was passed through a basin and the mixture was distilled off, ice water was added, and the mixture was acidified with hydrochloric acid to precipitate crystals of the target product, A851.

Melting point 170-175°C Example 5 N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-1,s-dimethyl-5-dimethylsullephylpyrazole-4-
Synthesis of sulfonamide (compound 59
6) Sulfonamide 39 obtained in Reference Example 16? (0
, 186motl' according to the method of Example 1 to prepare N-(n-butylcarbamoyl)-1,3-dimethyl-5-chloropyrazole-4-sulfonamide 5
I got 761.

Melting point: 188°C. Next, add 55% sodium hydride 4.71 F (5) to 100 d of dimethylformamide, add 9.1 ml of benzyl mercaptan (0,074 mat l k
After adding the sulfonamide 15 obtained above?
(Added LO49motl little by little. Stirred at room temperature for several hours and then stirred at 70-80°C for 5 hours. Added to water after evaporating the solvent.

After all the insoluble matter is separated, the P solution is made acidic with hydrochloric acid.
N-(n-butylcarbamoyl)-1,6-dimethyl-5-benzylthiopyrazole-4-sulfonamide 19
1 was precipitated.

'eF, dThe obtained compound 19 F (0,04
79mat l Kl” dissolved in acetic acid 100rRt, 1
[Chlorine gas was blown in at 1 to 20°C for 1.5 hours. When poured into reaction water, N-(n-butylcarbamoyl)-
1,s-Dimethyl-5-chlorosulfo Next, dimethylamine 4r (i: dissolved in THF 50m/ml) was added to the above compound under water cooling, and stirred at room temperature for 5 hours.After the reaction, THF
i, dissolved in an aqueous potassium carbonate solution, removed insoluble matter, and acidified with hydrochloric acid to give N-(n-butylcarbamoyl+-1,S-dimethyl-5-dimethyly (0,
026mal l was precipitated.

Melting point: 165-164°C From the compound obtained above, 1,3-dimethyl-5-dimethylsulfonyl pyrazole-4-sulfonylisocyanate was synthesized according to the method of Examples 1 and 2, and 2-
The desired product was obtained by reaction with amino-4-methoxy-6-methylpyrimidine.

Melting point 215-217°C Example 6 N-((4,6-dimethylpyrimidine-2
-yl)aminocarbonyl]-1,3-dimethyl-5-
Synthesis of ethylthiopyrazole-4-sulfonamide (compound 7fL7421 N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-1,5-dimethyl-5-chlorpyrazole-4-sulfonamide ( Compound A85) 1.
5 t (0,0042 motl.

Ethyl mercaptan 0.4 f, sodium hydroxide 0
．． In addition to 67 Pi dimethylformamide 10
Stirred at ~70°C for 4 hours. After the reaction, the solvent was distilled off, added to ice water, and acidified with hydrochloric acid to obtain target crystal 1.
．． 2 f/ was precipitated. Melting point: 189-190°C (4) The following is added below the last line of Table 2 on page 79 of the specification.

(4) The following is additionally inserted after compound level 411 in Table 3 on page 90 of the specification.

(5) The following shall be inserted in the T of the last line of ML on page 94 of the specification.

Procedural amendment 1 Indication of the case 1982 Patent Application No. 142069 2 Name of the invention Pyrazole sulfonylurea derivative, its manufacturing process and herbicide containing the derivative 3 Person making the amendment Relationship with the case Patent applicant address 101 Chiyoda, Tokyo 3-7-14 Kanda Nishikicho
Correction order 1-1 I\1 Voluntary? lli Correct 5 Detailed explanation of the invention column 6 of the specification to be amended Contents of the amendment (1) Compound No. 459 in Table 1, page 42 of the specification
In the × section, correct 1”CH3J to “OCH3”.

(2) Is this a supplement to Table 1 on page 59 of the specification and the procedure submitted on March 7, 1981? di
Following Compound No. 774 described on page 4 of the official text, the following is added.

[ ” (2) The following is to be added after the last line of page 71 of the specification, following Reference Example 24 stated on page 9 of the written amendment submitted on March 7, 1988. replenish.

“Reference Example 25 5-methoxycarbonyl-1-methylpyrazole-4-
Synthesis of sulfonamide 25-I Synthesis of N-tert-butyl-1-methylpyrazole-4-sulfonamide 40f3 of tert-butylamine was added to 150 ml of tetrahydrofuran, and 1 was prepared according to Reference Example 9.
Methylpyrazole 4-sulfonyl chloride 24.6g
was added dropwise with cold Jilt. The reaction mixture was heated at room temperature.
-IV, II tTi The precipitated salt was separated out and the solution was washed with water.

After drying the rIl residue, the l volume was distilled off under reduced pressure, and the precipitated solid was separated by filtration and washed with ether to obtain the target compound 26.
．． []t+ (%1. Melting point 99-100°C251N
Synthesis of 5-carboxy-1-methylpyrazole-4-sulfonamide 1 to Tertiary Zo Chizuki 13g of N-tert-butyl-1-methylpyrazole-4-sulfonamide 1 to 300ml of anhydrous tetrahylofuran 1g I'AI
At -1-50 to -40°C n-)
- Kizanlyo? Pj, (1,6M) ]000m
1? fia lowered.

After dropping, stir at room temperature for 1 hour, then add carbon dioxide to -30°
The blowing process started at C and then continued for 7 blows over a period of 3 hours at room temperature.

Then add 150ml of ice water and then] 2N salt NJ,
Added I Eim I. After washing the current layer with water and drying it,
By distilling off the solvent and washing the precipitated solid with ether, open compound 11. h to i! It's l. Melting point 1
78-179℃ 253 Synthesis of 5-methoxycarbonyl 1-methylpyrazole-4-sulbonamide 2 after reaching saturation
The mixture was heated to reflux for a while. Then, the solvent was distilled off under reduced pressure and poured into ice water for 20 minutes.
0ml and 200ml of ethyl acetate were added and stirred. After washing the organic layer with water and drying, the solvent was distilled off, and the precipitated solid was separated by filtration and washed with ether-ethyl acetate to obtain 6.5 g of the target compound. Melting point 121-122°C Reference Example 26 Synthesis of 3(5)-methoxycarbonyl-5(3)-methylpyrazole 4-Sulbonamide Obtained from 3(5)-methoxycarbonyl-5(3)-methylpyrazole. (3) Compound tooth 76 described on page 16 of the procedural amendment submitted on March 7, 1982, which is supplementary to Table 2 and below on page 79 of the specification.
Following 8, add the following.

Claims (3)

[Claims] (1) General formula (I): [In the formula, A represents a hydrogen atom, a lower alkyl group represents a phenyl group, and B represents a hydrogen atom, a lower alkyl group, an aralkyl group, a lower alkyl group, a halogenated alkyl group ,
co, Ft (Ry-1 hydrogen atom, lower alkyl group,
-cH, CT (=CH, represents a hydrogen atom, a lower alkyl group and a phenyl group, R, represents a hydrogen atom, and represents a lower alkyl group), KornRs
(R1 represents a lower alkyl group, and n represents an integer of 0.i or 2.) M9 represents a lower alkyl group, a halogen atom,
Represents a phenyl group which may be substituted with a nitro group. C is a hydrogen atom, lower alkyl group, aralkyl group, low R
Alkoxy group, halogen JJX child, Co, R. (FI4 is a hydrogen atom, a lower alkyl group, -a 0H-
Oh. or -CH*Om (represents 1!H), (]oNg:: (R*d represents a hydrogen atom, lower alkyl group or phenyl group, R6 represents a hydrogen atom or lower alkyl group), 5 (0)nR, ("y represents a lower alkyl group, and represents an integer of 1.2.), 8QdJ':", CRa represents a hydrogen atom or a lower alkyl group, and 1~.R1 represents a lower represents an alkyl group) or a phenyl group which may be substituted with a lower alkyl group, a halogen atom, or a nitro group. X represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom, and Y represents a hydrogen atom, a lower alkyl group, a lower alkoxy & lower alkoxyalkyl 1cFzOCR,OF
,, hagen atom, 00)]00. R,, (R,. l RI+ each represents a hydrogen atom or a lower alkyl group), an alkylamino group or a dialkylamino group, and 22 is an N atom. Alternatively, it represents 0-R□ (R+tVi hydrogen atom, . . . may form a 5-membered ring structure containing an oxygen atom together with a rogogenated alkyl group or Y). ] A pyrazole sulfonylurea derivative represented by (2) The following formula (1): [In the formula, A represents a hydrogen atom, a lower alkyl group, or a phenyl group, and B represents a hydrogen atom, a lower alkyl group, an aralkyl group, a lower alkoxy group, a halogenated alkyl group, 0
0. R (RFi hydrogen atom, lower alkyl group, -OH
,OH=OH. or -0)], Oiii 01 (represents),
co3:: (R. represents a hydrogen atom, a lower alkyl group or a phenyl group, and R1 represents a hydrogen atom or a lower alkyl group.)
, 5(O)nR+ (RI represents a lower alkyl group, n represents an integer of 0 or 1.2) or a phenyl group which may be substituted with a lower alkyl group, a halogen atom, or a nitro group. C is a hydrogen atom, lower alkyl group, aralkyl group, low i
Alkoxy group, halogen atom. Co, Fi, (R represents a hydrogen atom or a lower alkyl group. -OH, OH= OH* or -OH, CiyoOH). 0ON=° (R1 represents a hydrogen atom, a lower alkyl group, \R6 or a phenyl group, and 8 represents a hydrogen atom or a lower alkyl group.), 5(0)nR. (Rr represents a lower alkyl group, , n represents an integer of 0°1.2), SO,N (H-(R represents a hydrogen atom or a lower alkyl group, and I represents a lower alkyl group) or a lower alkyl group, A pyrazole sulfonyl isocyanate derivative represented by the following formula (■): [X represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a 7- Represents an atom, YPi hydrogen atom, lower alkyl group, lower alkoxy group, lower alkoxyalkyl i, CFi. 00) 1. OF,, halogen atom, 0OHOO*R+
□ ("16.'I□R1゜represents a hydrogen atom or a lower alkyl group, respectively.)
, represents an alkylamino group or a dialkylamino group, and 2 is an N atom. or ""u (Ru is a hydrogen atom), rogenation/alkyl group or Y may form a five-membered mound structure containing an oxygen atom. ). ] Aminopyrimidine otake amine triazide represented by /
The general formula (1) is characterized by reacting with a derivative in an inert solvent (5-) [wherein A, B, O, X, Y and 2 have the same meanings as above. ] A method for producing a pyrazolesulfonylurea derivative represented by (3) General formula (■): [In the formula, A represents a hydrogen atom, a lower alkyl group, or a phenyl group, Bri hydrogen atom, a lower alkyl group, an aralkyl group, a lower alkoxy group, a halogenated alkyl group,
co, a (R is a hydrogen atom, a lower alkyl group, -OH
,0H=GH. Represents a nyl group, R1 is a hydrogen atom, -! This represents a lower alkyl group. ), 5(0)n8 (- represents a lower argyl group, n represents an integer of 0.1.2), as many lower alkyl groups as possible. ...Represents a phenyl group which may be substituted with a rogene atom or a nitro group. C is a hydrogen atom, a lower alkyl group, an aralkyl group, a lower alkoxy group, a halogen atom, co,
R, (R is a hydrogen atom, a lower alkyl group, -0T(
, open=CH, or -cH, ayoOH. ),
CON Pi" (Rs6 represents a hydrogen atom, a lower alkyl group, or a phenyl group, [(, represents a hydrogen atom or a lower alkyl group.)
, 5(o)nRy (Ry is a lower alkyl group (~, n represents an integer of 0.1.2), So, N
8. ("s is a hydrogen atom or R represents a lower alkyl group, R6 represents a lower alkyl group) or a phenyl group optionally substituted with a lower alkyl group, a halogen atom, or a nitro group. .X represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom;
is a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower alkoxyalkyl group, CF+, 00H*OF,
, norogen atom, 0OHOO,R,, (R,o,
R,, are each hydrogen Ro. Represents an atom or lower alkyl group. ), alkylamino group or sialgylamino group, °z is an N atom or 50-R□ (R1, is a hydrogen atom, a halogenated alkyl group, or forms a five-membered structure containing an oxygen atom with Y) ). ] A herbicide characterized by containing one or more pyrazolesulfonylurea derivatives represented by the following as an active ingredient.