JPH0256469A - Pyridazinone derivative and herbicide - Google Patents

Abstract

NEW MATERIAL:A compound of formula I [R is formyl, COOR<1> (R<1> is H, lower alkyl, lower alkoxyalkyl or lower alkylthioalkyl); X is, halogen or lower alkyl; Z is methine or N] and a salt thereof. EXAMPLE:8-Formyl-7-(4,6-dimethoxypyrimidin-2-yl)oxyquinoline. USE:An active ingredient for herbicides. The compound of formula I exhibits excellent herbicidal effects against annual weeds and perennial weeds generating in upland fields and paddy fields but is highly safe for crops, especially wheat. The dosage of the compound of formula I is 0.01-1kg/10a as the active ingredient. PREPARATION:A compound of formula II is reacted with a compound of formula III (Y is halogen or methane sulfonyl) in the presence of a base such as K2CO3 in a solvent such as dimethylformamide at 10-200 deg.C for 1-30hr to provide the compound of formula I wherein R is formyl.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention provides a novel pyrimidine derivative useful as a herbicide.

and a herbicide characterized by containing this as an active ingredient.

[In the formula, R is a formyl group, ゛ or a group COOR' (wherein R' represents a hydrogen atom, a lower alkyl group, a lower alkoxyalkyl group, or a lower alkylthioalkyl group)
, X represents a hydrogen atom, a halogen atom, or a lower alkyl group, and Z represents a methine group or a nitrogen atom] and salts thereof.

(2) General formula rIn the formula, R is a formyl group or a group C0OR'' (in the formula R
1 represents a hydrogen atom, a lower alkyl group, a lower alkoxyalkyl group, or a lower alkylthioalkyl group), X represents a hydrogen atom, 5 a halogen atom, or a lower alkyl group, and Z represents methi (prior art). It is known that 2-phenoxypyrimidine derivatives are effective as pj11 herbicides [Unexamined Japanese Patent Application Publication No. 1983-1971]
55729, JP-A-62-174059, and Agricultural and Biological Chemistry Vol. 30, No. 59, p. 896 (196
6th year)].

(Problems to be solved by the invention) However, these compounds have weak herbicidal activity against annual weeds and hardly any activity against perennial weeds, and although they have strong herbicidal activity, they have no effect on some useful crops. However, there are disadvantages such as the fact that some of them cause drug damage.

The present inventors conducted extensive research on pyrimidine derivatives with the aim of developing compounds with excellent herbicidal activity without causing phytotoxicity to useful crops. The present invention was completed based on the discovery that it exhibits excellent herbicidal effects against not only weeds but also perennial weeds and is highly safe against one crop, especially wheat.

(Means for Solving the Problems) The pyrimidine derivative of the present invention has the general formula [wherein R is a formyl group, or a group C00R' (wherein ah is a hydrogen atom, a lower alkyl group, or a lower alkoxyalkyl group).

or lower alkylthioalkyl group), X
represents a hydrogen atom, a halogen atom, or a lower alkyl group, and Z represents a methine group or a nitrogen 1/4 atom.] The compounds of the present invention include salts thereof. Salts include alkali metal salts, alkaline earth metal salts, transition gold scrap salts and organic amine salts.

In the above general formula, the lower alkyl group of R is a methyl group,
Ethyl, propyl, and isopropyl groups are used as lower alkoxyalkyl groups, methoxymethyl, methoxyethyl, and ethoxyethyl groups are used as lower alkoxyalkyl groups, and methylthiomethyl, methylthioethyl, and ethylthioethyl groups are used as lower alkylthioalkyl groups. can be mentioned. The halogen atom of X is a fluorine atom, chlorine atom, bromine atom or iodine atom, and the lower alkyl group is a methyl group,
Examples include ethyl, propyl, and isopropyl groups.

Preferred compounds of the present invention represented by the above general formula include R being a formyl group or a group C0OR' (in the formula R1
is water SX child, alkyl group having 1 to 3 carbon atoms, and 1 to 6 carbon atoms
represents an alkoxyalkyl group or an alkylthioalkyl group having 1 to 6 carbon atoms, these alkyl groups may be linear or branched),
Examples include pyrimidine derivatives in which a halogen atom or a lower alkyl group is represented, and Z represents a methine group or a nitrogen atom, and salts thereof. Furthermore, R is a formyl group.

or a carboxyl group, where X is a hydrogen atom, a halogen atom,
or a methyl group, and pyrimidine derivatives and salts thereof in which Z is a methine group or a nitrogen atom are particularly preferred.

Next, the compounds of the present invention represented by the above general formula are illustrated in Table 1. In addition, the compound number will be referred to in the following description.

The compounds of the present invention with the general formula shown in Table 1 can be produced by the following method.

(Method A) A compound represented by the general formula (wherein, X and 2 have the same meanings as above) and a compound represented by the general formula (wherein, Y represents a halogen atom or a methanesulfonyl group) The compound represented by the general formula (wherein X and Z have the same meanings as above) is reacted with a compound represented by the general formula (wherein, Compounds can be produced.

Here, the bases include sodium hydroxide, potassium carbonate,
Organic or inorganic bases such as sodium hydrogen carbonate, triethylamine, dimethylamine, and pyridine can be used.

In addition, as a solvent, acetone, acetonitrile, methyl ethyl ketone, tetrahydrofuran, dimethyl formamide, dimethyl acetamide, dimethyl sulfoxide, benzene, toluene, chlorobenzene, dichloromethane,
Chloroform etc. can be used.

(Method B) In the presence of a base, a halogenated alkyl derivative represented by the general formula,
React in a solvent at a temperature of -10°C to 50°C for 1 to 10 hours (wherein, X and Z have the same meanings as above)
Potassium permanganate, chromic acid, potassium dichromate, silver oxide, hydrogen peroxide, tar-butyl hypochlorite.

In an organic or organic oxidizing agent such as perbenzoic acid or nitric acid and a solvent such as water, alcohol, acetic acid, acetone, or benzene, in the presence or absence of a base such as sodium hydroxide or sodium carbonate at -10°C. A compound represented by the general formula (wherein X and Z have the same meanings as above) can be prepared by reacting at a temperature of ~200°C for 1 to 30 hours. Here, the base and solvent used in Method A can be used.

(Method D) A compound represented by the general formula (wherein X and Z have the same meanings as above) can be produced.

(Method C) A compound represented by the general formula (wherein, X and 2 have the same meanings as above) and 2X'-R" (wherein, Xl represents a halogen atom.

R'' represents an alkyl group or an alkylthioalkyl group)
(wherein,
The organic or inorganic salt of the carboxylic acid derivative described above can be produced by reacting at a temperature of 0° C. for 1 minute to 20 hours.

Here, the bases include sodium hydroxide and potassium hydroxide.

Alkali metal or alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, sodium carbonate,
Carbonates such as potassium carbonate, ammonia, primary or secondary amines such as ethylamine, isopropylamine, dimethylamine, dimethylamine, and diethylamine can be used.

(Method E) The inorganic salt of the carboxylic acid derivative is prepared by adding an aqueous sodium hydroxide solution of equimolar amount to the compound represented by the following general formula (in the formula, X and 2 have the same meanings as above) at room temperature. After the reaction, a metal halide such as magnesium chloride, cupric chloride, calcium chloride, etc. is added, and the mixture is heated in a solvent such as water or alcohol at a temperature of 10°C to 200”C for 1 minute to
It can be produced by reacting for 20 hours.

In the following, the method for producing the compound of the present invention will be described with reference to Examples.

Example 18 - Synthesis of formyl-7-(4,6-cymethoxypyrimidin-2-yl)oxyquinoline 3-0 g (0,017 mol) of 8-formyl-7-hydroxyquinoline, and 2-fluoro-4, 6-cymethoxypyrimidine,
After dissolving 4.8 g (0,025 mol) of potassium carbonate in 80 mg dimethylformamide, 3.5 g (0,025 mol) of potassium carbonate
0,025 mol) was added thereto, and stirring was continued at 80 to 100°C for 7 and a half hours. After cooling, the reaction solution was diluted with 200ml of saturated saline.
200 mQ of ethyl acetate was added thereto, and the mixture was stirred at room temperature. After filtering off insoluble materials, the organic layer was separated. The organic layer was washed with saturated brine and then dried over anhydrous sodium sulfate. After filtering off the drying agent, the filtrate was concentrated. The precipitated crystals were harvested and washed with a small amount of chloroform. The filtrate portion was subjected to column chromatography using a mixed solvent of chloroform and ethyl acetate (19:1) and combined with the previous crystals to obtain 1.7 g of the title compound as pale yellow crystals.

Melting point 171-174°C Example 2 Synthesis of 8-bromo-2-(4,6-cymethoxypyrimidin-2-yl)oxy-1-naphthoic acid 8-bromo-2-(4,6-cymethoxypyrimidin-2-yl) (2-yl)oxy-1-naphthaldehyde 5.1 g (o, o
After dissolving 3 moles of potassium permanganate in 300 mA of acetone, 2.4 g of potassium permanganate (o, o 1
A potassium permanganate solution in which 5 mol) was dissolved in 500 mM water was gradually added dropwise, and stirring was continued for 16 hours. 6. The reaction solution was filtered, the filtrate was washed with ethyl acetate, and the aqueous layer was made acidic with acetic acid. Extracted three times with 100 rr+l of ethyl acetate.

The ethyl acetate layer was washed with water and then dried over anhydrous sodium sulfate. After filtering off the desiccant, the filtrate was concentrated, and the resulting solid was recrystallized from a mixed solvent of n-hexane and ethyl acetate to obtain 2.1 g of the title compound as colorless crystals.

Melting point 153-156°C Example 3 Synthesis of 2-(4,6-cymethoxypyrimidin-2-yl)oxy-1-naphthoic acid 2-(4,6-Simethoxypyrimidin-2-yl)oxy-1-naphthoic acid After dissolving 3.1 g (0,001 mol) of aldehyde in 100 ml of acetone, a potassium permanganate solution prepared by dissolving 1.6 g (0,001 mol) of potassium permanganate in 100 m Q of water was gradually added at room temperature. and continued stirring for 4 hours.

Pour the reaction solution into water, filter out the insoluble matter, and then reduce the filtrate to 10%
The mixture was acidified with hydrochloric acid and extracted three times with 100 mL of ethyl acetate. The ethyl acetate layer was further washed with saturated brine and dried over anhydrous sodium sulfate. After filtering off the drying agent, the filtrate was concentrated, and the resulting solid was washed with ether to obtain the title compound 1,
1. g was obtained as a colorless powder.

Melting point 125-126°C Example 4 7-(4,6-cymethoxypyrimidine-2-
Synthesis of 8-formyl-7-(4,6-cymethoxypyrimidin-2-yl)oxy-1-quinoline 1.9 g (0,006 mol)
After dissolving in 50 mA of acetone, 1.0 g (0,006 mol) of potassium permanganate was dissolved in 50 mA of water at room temperature.
Gradually remove the potassium permanganate solution dissolved in
The reaction solution that had been stirred for 17 hours was poured into water, the insoluble matter was filtered off, the aqueous layer was washed with ethyl acetate, and the aqueous layer was poured into water for 17 hours.
% hydrochloric acid and extracted three times with 50 mL of ethyl acetate. The ethyl acetate layer was further washed with saturated brine and dried over anhydrous sodium sulfate. After filtering off the drying agent, the filtrate was concentrated, and the obtained solid was washed with chloroform to obtain the title compound 0.
．． 7 g was obtained as a pale yellow powder.

Melting point: 170°C Example 5 Synthesis of methoxymethyl 2-(4,6-cymethoxypyrimidin-2-yl)oxy-1-naphtonite 2-(4,6-cymethoxypyrimidin-2-yl) was added to 50 mQ of dimethylacetamide. ) Oxy-1-naphthoic acid 2°Og (0,006 mol) and sodium hydrogen carbonate 1.7g (0°02 mol), and then suspended in chloromethyl methyl ether 0.8g (0,01 mol) at room temperature. mol) was gradually added dropwise and stirring was continued for 1 hour. The reaction solution was poured into water and extracted three times with 50 mA of ethyl acetate.
The ethyl acetate layer was washed with saturated brine and dried over anhydrous sodium sulfate. After filtering off the desiccant, the filtrate was concentrated, and the resulting solid was mixed with n-hexane and ethyl acetate (4: l).
2.1 g of the title compound was obtained as colorless crystals.

Melting point 85-86°C Example 6 2-(4,6-cymethoxypyrimidine-2
-yl) Synthesis of potassium oxy-1-naphthoate 0.6 g (0.01 mol) of potassium hydroxide in 50 mfl of water
3.3 g of 2-(4,6-simethoxypyrimidin-2-yl)oxy-1-naphthoic acid at room temperature.
(0.0 g mol) was added, and the 9 reaction solution was stirred for 2 hours and concentrated to obtain 3.6 g of the title compound as a colorless powder.

Example 7 7-(4,6-Simethoxypyrimidine-2
Synthesis of isopropylamine)oxyquinoline-8-carboxylate After dissolving 6 g (0,0 1 mol) of isopropylamine in 50 mm of water, 7- (4,6-
Cymethoxypyrimidin-2-yl)oxyquinoline-8
- Add 1.0 g (0°003 mol) of carboxylic acid,
The reaction solution, which had been stirred for an hour, was concentrated to yield the title compound 1.
6 g was obtained as a pale yellow viscous liquid.

Example 8 7-(4,6-cymethoxypyrimidine-2
Synthesis of calcium oxyquinoline-8-carboxylate (0.2 g (0,005 mol) of sodium hydroxide in 1 mol of water
After dissolving in 0 mQ, 1111.6 g (0°005 mol) of 7-(4,6-simethoxypyrimidin-2-yl)oxyquinoline-8-carvone was added and dissolved at room temperature, followed by 0.58 g of calcium chloride. (0,005
mol) was dissolved in 10 mg of water, and stirring was continued for 5 minutes. The precipitated crystals were collected by filtration to obtain 1.6 g of the title compound as a white powder.

The herbicide of the present invention contains the compound of the present invention as an active ingredient. 6 When the compound of the present invention is used as a herbicide, the herbicide of the present invention has a decomposition point of 169-173°C. A carrier, a surfactant, a dispersant, an auxiliary agent, etc. can be blended and used in various forms such as a wettable powder, an emulsion, or a powder.

Examples of carriers include solid carriers such as dicrite, talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, and urea, and liquids such as isopropyl alcohol, xylene, cyclohexanone, and methylnaphthalene. Examples include carriers. Examples of surfactants and dispersants include alcohol sulfate ester salts, alkylaryl sulfonates, lignin sulfonates, polyoxyethylene glycol ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene sorbitan monoalkylates, and the like. It will be done. Examples of adjuvants include carboxymethylcellulose, polyethylene glycol, gum arabic, and the like. When using it, it can be diluted to an appropriate concentration and sprayed, or it can be applied directly.

The compound of the present invention is applied to soil or foliage in fields before or after weed germination. In addition, in paddy fields, the herbicide of the present invention, which is applied to flooded soil or to foliage before or after weed germination, is applied in an amount of 0.01 g to 1 kg per 10 ares as an active ingredient. When spraying on plant foliage, it is diluted to 0.1 to 110,000 pp. Furthermore, the compounds of the present invention can also be used in combination with other herbicides.

Below, in the margin, an example of the herbicide formulation of the present invention will be given. In addition,
% indicates weight percentage.

Example 9 Wettable powder compound (1) 10%, Emulgen 810 (registered trademark of Kao Corporation) 0.5%, Demol N (registered trademark of Kao Corporation) 0.5%, Kunilite 201 (registered trademark of Kunimine Industries Co., Ltd.) W) 20% and 69% of Zikrite CA (Zikrite Co., Ltd. registered trademark) were uniformly mixed and pulverized to prepare a wettable powder.

Example 10 Emulsion An emulsion was prepared by uniformly dissolving 30% of compound (12), 20% of cyclohexanone, 11% of polyoxyethylene alkylaryl ether, 4% of calcium alkylbenzenesulfonate, and 35% of methylnaphthalene.

Example 11 Granule Compound (1) 5%, sodium salt of lauryl alcohol sulfate 2%, sodium lignin sulfonate 5%
, carboxymethyl cellulose 2%, and clay 86%
Mix and grind evenly. Add 20 parts by weight of water to 100 parts by weight of this mixture, knead it, and use an extrusion type granulator for 14 hours.
After processing into granules of ~32 meshes, they were dried to form granules.

Example 12 Powder 2% of compound (16), ±5% of diatoms, and 93% of clay were uniformly mixed and ground to obtain a powder.

(Effects of the Invention) The compound of the present invention can be applied to barnyard grass, crabgrass, and blackberry grass that occur in fields.

Foxtail, bluegrass, sycamore, sycamore, oat, Italian ryegrass, and Japanese knotweed.

Annual weeds such as whiteweed, pigweed, Japanese thornweed, American redweed, Japanese thistle, Ebisugusa, chickweed, Noassagao, Ona fir, Kogomega spp., Japanese millet 1-inch grass, Uma no chahiki, Yaemegura, buckwheat, Wildflower, American helium, and other annual weeds; Perennial weeds such as johnson grass, staghorn grass, and grasshopper can also be effectively controlled. In addition, annual weeds such as Japanese grasshopper, Japanese cypress, Japanese cypress, Japanese fireweed, Helaomodaka and other annual weeds that occur in rice fields and θ watermelon! It can effectively control perennial weeds such as Haurikawa and Kurogwai. On the other hand, it is highly safe for crops and other products, especially for wheat.

Next, the effects of the compounds of the present invention will be explained using test examples. The comparative compounds in the test examples are as follows.

Comparative compound 1 2-(4,6-cymethoxypyrimidin-2-yl)oxybenzoic acid (compound described in JP-A-62-174057) Comparative compound 2 3-(5-chloropyrimidin-2-yl)oxybenzoic acid Comparative compound 35-(5-chloropyrimidin-2-yl)oxy-
Ethyl 2-nitrobenzoate (compound described in JP-A-54-55729) Comparative compound 44.6-dimethyl-2-(m-tolyloxy)pyrimidine [Agricultural and Biological Chemist Vol. 9430, No. 9, Compounds described on page 896 (1966)] Test Example 1 Field crop foliage treatment test In a 100-pot filled with soil, barnyard grass (Ech), Japanese knotweed (Dig), Japanese knotweed (Pol), and Japanese blueberry (
Asa), Che and Cy
Each seed of i) was sown and covered with soil to a thickness of 0.5 to 1 inch. After the pots were grown for two weeks in a glass room at 20 to 25°C, a predetermined amount of a hydrating powder prepared according to Example 9 was diluted with water and sprayed on the leaves at a rate of 10 (l/10 are).

The investigation was conducted on the 14th day of drug treatment according to the criteria in Table 2.

The results are shown in Table 3 as an index.

(Note) Test plants are indicated by abbreviations. The same applies to subsequent tables.

Test Example 2 Field Crop Soil Treatment Test Seeds of Japanese barnyard grass, UV>, Japanese knotweed, whiteweed, and Kogomega cyperus were sown in 100-pots filled with soil,
It was covered with soil to a thickness of 0.5 to 11 degrees. On the day after sowing, a predetermined amount of the wettable powder prepared according to Example 9 was diluted with water and sprayed on the soil surface at a rate of 100 g per 10 are. The investigation was conducted on day 20 of drug treatment according to the criteria in Table 2. The results are shown in Table 4 as an index.

Test Example 3: Effect test on perennial weeds Tubers of lily pads were placed in a 100 d pot filled with soil, and 0.5 to 1
1 was covered with soil. Place the pot in a glass room at 20-25℃.
After growing for a week, a predetermined amount of the wettable powder prepared according to Example 9 was diluted with water and sprayed on the leaves at a rate of 10011 per 10 are. The W4 examination was conducted on the 3rd and 114th day of the drug clinic. The results are shown in Table 5 as an index according to the criteria in Table 2.

Seeds of buckwheat and buckwheat (Poc) were sown, and 0.5~
1 o was covered with soil. After the pots were grown in a glass room at 20 to 25°C for two weeks, a predetermined amount of the wettable powder prepared according to Example 9 was diluted with water and sprayed on the leaves at a rate of 100 Q per 10 are.

The investigation was conducted on day 20 of drug treatment. The results are shown as indexes in Table 7 for herbicidal effects according to the standards in Table 2 and chemical damage according to the standards in Table 6.

Test Example 4 Selectivity Effect Test on Wheat Wheat, Japanese knotweed (Pop), Japanese radish (Asa), Japanese radish (chθ), and Japanese radish (Raρ) were placed in a 600-pot filled with soil.

Test Example 5 Paddy field weed control test After filling a 100 ci bottle with paddy soil and raking it,
Seeds of each type (n) and firefly (Sci) were sown and flooded in 31. Two days after sowing, according to Example 9'! Aat,
A predetermined amount of the wettable powder was diluted with water, and the water surface was treated with the active ingredient at a rate of 100 g per 10 ares. The Li test was carried out on day 21 after drug treatment according to the criteria in Table 2. 8th result
It is shown in the table as an index.

Procedural amendment Procedural amendment 2nd day of the needle month in 1986 1. Display of incident 1986 Patent Original No. 310741 2. Name of the invention Pyrimidine derivatives and herbicides 3. Person who makes corrections Relationship with the incident

Claims (2)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R is a formyl group or a group COOR^1 (in the formula R
^1 represents a hydrogen atom, a lower alkyl group, a lower alkoxyalkyl group, or a lower alkylthioalkyl group. ), X represents a hydrogen atom, a halogen atom, or a lower alkyl group, and Z represents a methine group or a nitrogen atom. ] A pyrimidine derivative and its salt. (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R is a formyl group or a group COOR^1 (in the formula R
^1 represents a hydrogen atom, a lower alkyl group, a lower alkoxyalkyl group, or a lower alkylthioalkyl group. ), X represents a hydrogen atom, a halogen atom, or a lower alkyl group, and Z represents a methine group or a nitrogen atom. ] A herbicide characterized by containing a pyrimidine derivative represented by the following and its salt as an active ingredient.