JPS6137782A - Pyrazolesulfonylurea derivative, its preparation and selective herbicide - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I (R<2> and R<2> are lower alkyl; X and Y are lower alkyl, or lower alkoxy; Z is N, or -CH=). EXAMPLE:N-[( 4-Methoxy-6-methylpyrimidin-2-yl-( aminocarbonyl ]-3-methoxy-4- ethoxycarbonyl-1-methylpyrazole-5-sulfonamide. USE:A selective herbicide. In either case of soil treatment or foliar treatment, it shows strong herbicidal power on various weeds, and shows high safety to important crops such as rice plant, wheat, cotton, etc. Since it shows high activity with a small amount of it, it is useful as a herbicide for orchards and nonagricultural lands. PREPARATION:A pyrazolesulfonyl isocyanate derivative shown by the formula II is reacted with a pyrimidine or triazone derivative shown by the formula III in an inert solvent such as fully dried dioxane, acetonitrile, etc., to give a compound shown by the formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel pyrazolesulfonylurea derivative, a process for producing the compound, and a selective herbicide containing the compound as an active ingredient.

It is essential to use herbicides to protect important crops such as rice, wheat, and cotton from weed damage and increase yields. Particularly in recent years, in arable land where these useful crops and weeds coexist, there has been a demand for selective herbicides that can selectively kill only weeds without causing chemical damage to crops even when applied to the foliage of crops and weeds simultaneously. It is rare. In addition, from the viewpoint of preventing environmental pollution and reducing economic costs during transportation and spraying, search research has been carried out for many years to find compounds that have a high herbicidal effect with as low a dose as possible. Although some compounds with such properties are currently used as selective herbicides,
There is also a need for new compounds that still have these properties.

In order to develop herbicides that are selective for important crops, the present inventors have continued to research for many years, and in order to produce compounds with higher herbicidal power and selectivity, we have developed a number of herbicides that can be used to kill weeds. We have considered the characteristics. As a result, a compound of the general formula (I) [wherein R1 and R2 represent a lower alkyl group] was obtained.

X and Y each independently represent a lower alkyl group or a lower alkoxy group, and Z represents a nitrogen atom or a -CH= group. ] The pyrazole sulfonylurea derivative (hereinafter referred to as the compound of the present invention) represented by has a strong herbicidal power against many weeds in both soil treatment and foliage treatment, and is effective against important crops such as rice, wheat, The present invention was completed after discovering that the product has high safety against cotton. On the other hand, the compounds of the present invention are also useful as herbicides for orchards and non-cultivated land because they exhibit high herbicidal activity at a much lower dose than conventional herbicides.

As a prior art having a structure similar to the compound of the present invention, for example, European Patent Application Publication No. 87.780 describes a substituent of an alkoxy group at the 3-position, which is a characteristic of the compound of the present invention.
Compounds having an alkyl group at the 3-position are disclosed. but,
The compound of the present invention is not specifically disclosed and is a new compound. The present inventors have completed the present invention by discovering that by replacing the alkyl group at the 3-position with an alkoxy group, the selectivity for useful crops, especially the safety for cotton, can be significantly increased.

The compound of the present invention represented by the general formula (1) is a new compound, and can be easily produced by selecting one of the following reaction formulas 1 and 2.

Ruminant Dog [Formula R1, R2, X, Y and Z have the same meanings as above. ] That is, by dissolving the pyrazolesulfonylisocyanate derivative (II) in a sufficiently dried inert solvent such as dioxane or acetonitrile, and adding thereto a pyrimidine or triazine derivative represented by formula (DI) and stirring, In general, the compound of the present invention (
1) is obtained. If the reaction is difficult to proceed, use a suitable base such as triethylamine, triethylenediamine,
The reaction progresses easily by adding a small amount of pyridine, sodium alkoxide, sodium hydride, etc.

[In the formula, R1, RR, XSY and Z have the same meanings as above. R'' represents an alkyl group or a phenyl group. Compound (VI) is obtained by reacting with chloroformic acid ester or carbonic acid ester in the presence of a base such as potassium carbonate in a solvent such as methyl ethyl ketone, and treating with an acidic substance such as a reactive acid salt.Then, the compound (VI) is obtained in a solvent such as toluene. Compound (1) of the present invention can be obtained by heating with (II).

Pyrazole sulfonyl isocyanate (■) or pyrazole sulfonyl carbamate derivative (I), which is a raw material used in Reaction Formulas 1 and 2, is synthesized by pyrazole sulfonamide by the method described below, and further by the patent application filed in 1973.
It can be synthesized by referring to the methods described in JP-A No. 8-70407 and JP-A-55-13266.

A synthesis example of the intermediate pyrazole sulfonamide used in the present invention is described below as a reference example.

Synthesis of 3-methoxy-4-ethoxycarbonyl-1-methylpyrazole-5-sulfonamide (1) Synthesis of 3-methoxy-4-ethoxycarbonyl-1-methylpyrazole 4-ethoxycarbonyl-3- 10 g of hydroxy-1-methylpyrazole, 41.7 g of methyl iodide, 17.9 g of anhydrous potassium carbonate, and 20 g of dry methyl ethyl ketone.
The mixture was heated under reflux in 0ml for 15 hours.

After the reaction was completed, inorganic substances were separated by filtration while hot, and the solvent was distilled off under reduced pressure. The resulting combination was diluted in chloroform and 5
% caustic soda aqueous solution, sequentially dried with water, and after drying the solvent,
It was dried under reduced pressure. The obtained crude crystals were recrystallized from a mixed solvent of n-hexane-benzene to obtain 8.2 g of the desired product. Melting point: 87-88.5°C (2) Synthesis of 3-methoxy-4-ethoxycarbonyl-1-methylpyrazole-5-sulfonamide Dry 7.33 g of ethyl 3-methoxy-1-methylpyrazole-4-carboxylate. It was suspended in 225 ml of ether and cooled to -60°C or below. Then, an ether solution of lithium diisopropylamide (1.2 times the mole) was added dropwise. Stir as it is for 1 hour, then add sulfur dioxide gas for 30 minutes.
It blew for a minute. After stirring at -60'C for 1 hour, the precipitated crystals were filtered and dried to obtain 8.1 g of solid lithium 3-methoxy-4-ethoxycarbonyl-1-methylpyrazole-5-sulfonate.

Next, add this to 150+++1 ice water and 1 dichloromethane.
50I111 and 4.3 g of N-chlorosuccinimide were added at a temperature of 0-5°C. After stirring at room temperature for 30 minutes, the dichloromethane layer was separated, and the aqueous layer was further extracted with 100 IIll of dichloromethane and combined. Obtained 3-
Aqueous ammonia (28χ) prepared by cooling a dichloromethane solution of methoxy-4-ethoxycarbonyl-1-methylpyrazole-5-sulfonyl chloride to below 10°C
ml was added dropwise. After stirring at room temperature, the solvent was distilled off to obtain 2.7 g of the desired product. Melting point 131-133℃ Moxibustion Main Synthesis of N-(3-methoxy-4-ethoxycarbonyl-1-methylpyrazole-5-sulfonyl)methylcarbamate 3-methoxy-4-ethoxycarbonyl-1-methylpyrazole-5- Sulfonamide 2.51 g, ethyl chloroformate 1.25 g, anhydrous potassium carbonate 1.59
g was heated under reflux for 5 hours in 20 ml of dehydrated acetonitrile.

After the reaction was completed, the solvent was distilled off under reduced pressure, diluted with ice water, insoluble matter was filtered off, and the filtrate was acid washed with diluted hydrochloric acid. The precipitated crystals were filtered, washed with water, and dried to obtain 2.51 g of the desired product. Melting point: 99-101°C Specific synthesis examples of the compounds of the present invention will be described below using the intermediates obtained in the above reference examples, but the present invention is not limited thereto.

Farmers group, synthesis of N-((4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl-3-methoxy-4-ethoxycarbonyl-1-methylpyrazole-5-sulfonamide (compound dynamic magnetism 7) N-(3-methoxy-4-ethoxycarbonyl-1-methylpyrazole-5-sulfonyl)methylcarbamate 1.04 g (3,In+m
ol) and 0.42 g (3.1 mmol) of 2-amino-4-methoxy-6-methylpyrimidine in toluene 3
The mixture was heated under reflux for 2 hours at 0 m-1. After the reaction was completed, toluene was distilled off under reduced pressure, and the residue was allowed to stand overnight to crystallize. The crude crystals were thoroughly loosened by adding a small amount of acetonitrile, filtered, and then dried under reduced pressure to obtain 0.61 g of white target crystals. Melting point 158-160℃
.

Synthesis of large carbonyl N-((4,6-dimethoxypyrimidin-2-yl)aminocarbonyl-3-methoxy-4=ethoxycarbonyl-1-methylpyrazole-5-sulfonamide (compound 8) 3-methoxy -4-ethoxycarbonyl-1-methylpyrazole-5-sulfonamide 6.1
2.5 g of n-butyl isocyanate was added to a mixture of 4.6 g of anhydrous potassium carbonate and 50 ml of acetone at room temperature, and the mixture was heated under reflux for 3 hours. After the reaction was completed, acetone was distilled off under reduced pressure, the residue was poured into ice water, insoluble matter was filtered off, and the filtrate was precipitated with hydrochloric acid. The precipitated crystals were filtered, washed with water, and dried to give N-(n-butylcarbamoyl)-3-methoxy-4-ethoxycarbonyl-1-methylpyrazole-5.
- 4.5 g of sulfonamide were obtained. Melting point 125-128
C. Next, this was added to 100 ml of dry toluene, 4.0 g of phosgene was blown into the mixture under heating under reflux, and the mixture was further heated under reflux for 1.5 hours. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain 0.85 g of crude sulfonyl isocyanate.

0.85 g of this crude sulfonyl isocyanate was added to a solution of 0.35 g of 2-amino-4,6-simethoxypyrimidine in 20 ml of dry acetonitrile, and the mixture was stirred at room temperature.

The resulting crystals were filtered, washed, and dried to obtain 0.7 g of the desired product. Melting point: 142 DEG -143 DEG C. Examples of the compounds included in the present invention are shown in Table 1 below, along with the compounds synthesized in the above examples, but the compounds of the present invention are not limited to these.

Table 1 Me: methyl group Et: ethyl group.

When applying the compounds of the invention as herbicides, a suitable carrier is generally used, such as clay, talc, bentonite,
Solid carriers such as diatomaceous earth or water, alcohols (methanol, ethanol, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), chlorinated hydrocarbons, ethers, ketones, esters (ethyl acetate, etc.), It can be used in combination with liquid carriers such as acid amides (dimethylformamide, etc.), and if desired, emulsifiers, dispersants, suspending agents, penetrating agents, spreading agents, stabilizers, etc. can be added to form solutions and emulsions. It can be put to practical use in any desired dosage form, such as a wettable powder, powder, or granule.

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.

■Kadamaku Wettable powder Compound of the present invention 7 -------1・-1---
・-50 parts Sieglite A −・−・・・・・・・・・・
−・・−・・−・・46 parts (Kaolin clay: Sieglite Kogyo ■Product name) Tsurupol 503!1m−・−−
−−−−−−−−−−2 parts (mixture of nonionic surfactant and anionic surfactant: Toho Chemical ■trade name) Carplex (anticaking agent) −−−−−2 parts (White Carbon: Shionogi & Co., Ltd. trade name) The above is mixed and pulverized uniformly to make a wettable powder.

■ Gold±1 Wettable powder Compound of the present invention Dimension 8 −−−−−−−−−・−・−・・
Part 45 Sieglite A ・・・−・−・−−−−−
−−−−−−−−51 parts (Kaolin clay: Sieglite Kogyo ■Product name) Tsurupol 5039 ・・−・−
・－－－－－1－－・－・ 2 parts (Mixture of nonionic surfactant and anionic surfactant: Toho Chemical ■Product name) Carplex (anti-caking agent)--- At least 4 parts (white carbon: Shionogi & Co., Ltd. trade name) are mixed and pulverized uniformly to make a wettable powder.

Example B1 - Emulsion of the compound of the present invention 7 - - - - - - - 2 parts
Shinshin −−−−−−−−−−−−−−・
−−−−−−78 parts dimethylformamide ・−・−
...-15 part Tsurupol 2680 ----------...
-5 parts (mixture of nonionic surfactant and anionic surfactant; Toho Chemical ■ trade name) The above is mixed uniformly to form an emulsion. When used, the above emulsion is diluted 10 to 10.000 times and sprayed at an amount of active ingredient of 0.005 kg to 10 kg per hectare.

■Gold spots↓ Flowable compound of the present invention Nu7 -1---・--
25 parts Ageli Seal S -710---10 parts (
Nonionic surfactant; Kao Atlas ■Product name) Lunox 1000 G
0.5 parts (anionic surfactant: Toho Chemical ■trade name)
1% rhodobol water 4-・・−−−−−−−−−20
Part (thickener: Lone Boulin product name) Water −
・−−−−−−−・・・−・−・−−−−・−１−−・
-・---------44.5 parts or more are uniformly mixed to form a flowable agent.

``Tobi 5Ytai'' - Granules Compound of the present invention NIL8, ------1------
--- 0.1 part bentonite ---
-Concave--55.0 parts talc--
---------mon - - After uniformly mixing and pulverizing 44,9 parts or more, adding a small amount of water, stirring and kneading, granulating with an extrusion type granulator, drying and granulating. Make it into a drug.

ytachiko Granule Compound of the Invention Arashi 7 ---------1・-・----
−−・0.5 part bentonite −・・−−−
−−−−−−−−−−−55,0 parts talc
-...-- Granulate and dry to make granules.

Furthermore, the compound of the present invention may be applied in combination with other herbicides, various insecticides, fungicides, synergists, etc. when preparing or spraying, if necessary.

Other types of herbicides mentioned above include, for example, Farm Chemicals, Handbook (Farm (:chemical)).
sHandbook) 70th edition (1984).

The compound of the present invention can be used to control various weeds in agricultural and horticultural fields such as fields, paddy fields, and orchards, as well as in non-agricultural fields such as playgrounds, vacant lots, and railway edges, and the amount of application depends on the application situation. Although there are differences depending on the application period, application method, target grass species, cultivated crops, etc., the appropriate amount of active ingredient is generally about 0.005 to 10 kg per hectare.

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

μ”1 doctor:”-herbicidal effect test line 15C1 by soil treatment
1, horizontal 22011. Put sterilized diluvial soil in a plastic box with a depth of 6 cm+, and grow rice, wild grass, crabgrass, cyperus, japonica, leafminer, japonica,
Mixed sow cotton, about 1. After covering the soil with 5cn+ soil, the amount of active ingredient was uniformly spread over the soil surface in 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 2.

Some of the compounds of the invention have selectivity for certain crop species.

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% 1.--.Weed killing rate 5-20% 0-.-.Weed killing rate 5% or less (dove) However, the above-mentioned herbicidal rate was determined by measuring the weight of above-ground plants in the chemically treated area and above-ground plants in the non-treated area using the following formula.

In addition, tubers of Urikawa, Mizugaya cypress, and Kurogwai were placed in the beds. Furthermore, rice seedlings at the 2.5 leaf stage were transplanted. The next day, a diluted drug solution was dropped onto the water surface using a measuring pipette to a predetermined dose.

Three weeks after dropping 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.

Table 4 Procedural amendment 1 Indication of the case Patent application No. 159177 of 1982 2 Name of the invention Pyrazole sulfonylurea derivative, its manufacturing process and selective herbicide 3 Person making the amendment Relationship with the case Patent applicant address Chiyoda-ku, Tokyo Kanda Nishikicho 3-7-1 Name (
398) Nissan Chemical Industries, Ltd. 5 Number of inventions increased by amendment 06 Detailed explanation of the invention in the specification subject to amendment 7 Contents of the amendment (li On page 15, line 7 of the specification, “1-methylpyrazole- 5-sulfonyl)methyl" is corrected to "l-methylpyrazole-5-sulfonyl)ethyl."

(2) Insert the following additionally between lines 16 and 17 on page 12 of the specification tube.

Synthesis of (N-(3-ethoxy-4-ethoxycarbonyl-1-methylpyrazole-5-sulfonyl)ethyl carbamate) 3-ethoxy-4-ethoxycarbonyl-1-methylpyrazole- 5-sulfonamide was synthesized and then synthesized according to Reference Example 2. Melting point 95-9
(3) On page 15, line 6 of the specification, "1-methylpyrazole-5-sulfonyl)methyl" is corrected to "[1-methylpyrazole-5-sulfonyl)ethyl".

14) Table 1 on pages 15 and 16 of the specification is corrected as follows.

Procedural amendment February 18, 1985

Claims (4)

[Claims] (1) General formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R^1 and R^2 represent lower alkyl groups. X and Y each independently represent a lower alkyl group or a lower alkoxy group, and Z represents a nitrogen atom or a -CH= group. ] A pyrazolesulfonylurea derivative represented by. (2) General formula (II): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) [In the formula, R^1 and R^2 represent lower alkyl groups. ] A pyrazole sulfonyl isoryanate derivative represented by
The following formula (III): ▲Mathematical formulas, chemical formulas, tables, etc.▼(III) [In the formula, X and Y each independently represent a lower alkyl group or a lower alkoxy group, and Z is a nitrogen atom or -C
H= represents a group. ] General formula (I) characterized by reacting an aminopyrimidine or aminotriazine derivative represented by in an inert solvent: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R^ 1, R^2 represents a lower alkyl group. X and Y each independently represent a lower alkyl group or a lower alkoxy group, and Z represents a nitrogen atom or a -CH= group. ] A method for producing a pyrazolesulfonylurea derivative represented by (3) General formula (IV): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (IV) [In the formula, R^1 and R^2 represent lower alkyl groups. R^3 represents a lower alkyl group or a phenyl group. [In the formula, X and Y each independently represent a lower alkyl group or a lower alkoxy group, Z is a nitrogen atom or -C
H= represents a group. ] General formula (I) characterized by reacting an aminopyrimidine or aminotriazine derivative represented by in an inert solvent: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R^ 1, R^2 represents a lower alkyl group. X and Y each independently represent a lower alkyl group or a lower alkoxy group, and Z represents a nitrogen atom or a -CH= group. ] A method for producing a pyrazolesulfonylurea derivative represented by (4) General formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R^1 and R^2 represent lower alkyl groups. X and Y each independently represent a lower alkyl group or a lower alkoxy group, and Z represents a nitrogen atom or a -CH= group. ] A selective herbicide characterized by containing one or more pyrazolesulfonylurea derivatives represented by the following as an active ingredient.