JPH04108777A - Pyrimidine derivative and herbicide - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I [X is nitro, alkyl(thio), halogen, acyl, alkoxycarbonyl, (substituted) phenylthio, pyrrole, etc.; R is H, alkyl or benzyl; (n) is 1 or 2 with the proviso that when X is alkyl or halogen, (n) is 2]. EXAMPLE:6-Acetyl-2-(4,6-dimethoxypyrimidin-2-ylthio)benzoic acid. USE:A herbicide. PREPARATION:A compound shown by formula II is made to react with a compound shown by formula III [Y<1> is halogen, alkylsulfonyl or (substituted) benzylsulfonyl] in the presence of a base (e.g. metal sodium or anhydrous potassium carbonate) preferably in an inert solvent (e.g. benzene) for 1-24 hours.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a novel pyrimidine derivative, a salt thereof, and a herbicide containing the same as an active ingredient and which can be applied to rice fields, fields, non-agricultural land, etc. .

(Prior art) Specification of JP-A-62-174059, JP-A-54-
5.5729 and Agricultural and Biological Chemistry (Agricultural and Biological Chemistry)
Ural and Biological Ch.
volume 30, issue 9, page 896 (19
1966) describes that 2-phenoxypyrimidine derivatives and 2-phenylthiopyrimidine conductors have herbicidal activity.

(Problems to be Solved by the Invention) However, the compounds described in these documents have insufficient unveiling effects or have problems in terms of safety for some crops.

As a result of intensive research into pyrimidine compounds with the aim of developing further improved compounds, the present inventors found that
The compound of the present invention, which has a substituent at a specific position on the pyrimidine ring and benzene ring of a phenylthiopyrimidine conductor, exhibits excellent herbicidal effects against annual weeds as well as perennial weeds, and is safe for crops, especially cotton. They found that it has high properties and completed the present invention.

(Means for Solving the Problems) The pyrimidine rust conductor of the present invention has the general formula (wherein, an alkoxyalkoxy group, a phenoxyalkoxy group, an alkoxyalkylthio group, an alkyl group, or a phenylthio group optionally substituted with a halogen atom, a virol group, or a cycloalkylalkoxy group, R represents a hydrogen atom, an alkyl group, or a benzyl group, and n indicates an integer of 1 or 2. However,

When X represents an alkyl group or a halogen atom, n represents 2. ).

Further, when R in the general formula [I] is a hydrogen atom, it may be in a free form or in a salt form. These salts include alkali metal salts, alkaline earth metal salts, transition metal salts, and organic ammonium salts.

The compounds of the present invention represented by the general formula [11] are illustrated in Table 1. Note that the compound number will be referred to in the following description.

(The following is a blank space) Table 1 Table 1 continued The compound of the present invention can be produced according to the following method.

[Rule [1111[1] (In the formula, Y" is a halogen atom, an alkylsulfonyl group,
It represents a benzylsulfonyl group or a substituted benzylsulfonyl group, and X, R and n have the same meanings as above. ) That is, the compound of the present invention represented by the formula [the formula (U]
It can be produced by reacting the compound represented by the formula [III] with the compound represented by the formula [III] in the presence of a base, preferably in an inert solvent, at a temperature ranging from room temperature to the cloudy point of the solvent for 1 to 24 hours. can. When the reaction is carried out without a solvent, an alkali metal carbonate such as anhydrous potassium carbonate is used as a base, and the reaction is carried out within a temperature range of 120 to 160°C.

Examples of solvents include hydrocarbon solvents such as benzene, toluene, and xylene, halogenated hydrocarbon solvents such as methylene chloride and chloroform, alcohol solvents such as methanol, ethanol, and 2-propanol, diethyl ether, isopropyl ether, tetrahydrofuran, 1.4
- Ether solvents such as dioxane, ketone solvents such as acetone and methyl ethyl ketone, ester solvents such as methyl acetate and ethyl acetate, aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide. Solvents such as acetonitrile and water can be used. In addition, bases include alkali metals such as sodium metal and potassium metal, alkali metal hydrides and alkaline earth metal hydrides such as sodium hydride, potassium hydride, and calcium hydride, sodium carbonate, potassium carbonate, and calcium carbonate. , carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, and metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide.

The compound of the present invention can also be produced by the following method.

[IVl [V] [V[]
(In the formula, R, A diazonium salt EV] is produced from the aniline derivative represented by the formula [IV), and the diazonium salt [V]
It can be produced by reacting with a compound represented by formula [VI]. As a diazonium salt,
In addition to hydrochloride, there are hydrobromide, hydroiodide, tetrafluoroborate, and sulfate. Moreover, a basic solution can be produced by adding strong bases such as sodium hydroxide, potassium hydroxide, barium hydroxide, and calcium hydroxide to a solvent.

2-(4,6-Simethoxypyrimidin-2-ylthio)benzoic acid produced as above is reacted with equal amounts of baking soda, sodium hydroxide, potassium hydroxide, sodium hydride, etc. in alcohol or water. can be made into an alkali metal salt.

Moreover, an alkaline earth metal salt can be obtained by reacting an alkali metal salt with calcium chloride or reacting the corresponding benzoic acid with calcium carbonate or calcium hydride. Furthermore, a transition metal salt such as iron can be obtained by reacting an alkali metal salt with iron chloride or the like.

Furthermore, primary amines, secondary amines, tertiary amines,
An organic ammonium salt can be obtained by reacting aliphatic amines such as jetanolamine, triethanolamine, alkoxyalkylamine, cyclohexylamine, and morpholine, or aromatic amines such as aniline and naphthylamine.

Next, the method for producing the compound of the present invention will be specifically explained with reference to Examples.

Example 1 Synthesis of 6-acetyl-2-(4,6-cymethoxypyrimidin-2-ylthio)benzoic acid (compound 8) After making a diazonium salt with 2.3 g of sodium nitrate, this diazonium salt was converted into a previously prepared aqueous sodium disulfide solution (prepared from 8.3 g of 9-hydrated sodium sulfide, 1.1 g of sulfur, 2.6 g of sodium hydroxide, and 15 mg of water). ) was gradually added dropwise at 0 to 5°C.

After the dropwise addition was completed, the mixture was stirred at room temperature for 2 hours to complete the reaction.

The reaction solution was poured into a large amount of water, concentrated hydrochloric acid was added thereto, and then extracted with ethyl acetate. An aqueous sodium hydrogen carbonate solution was added to the ethyl acetate layer to extract the sodium hydrogen carbonate soluble content. 7.0 g of sodium pyrosulfate was added to this aqueous solution, and the mixture was refluxed for 30 minutes to complete the reaction.

After adding concentrated hydrochloric acid to the reaction solution, the mixture was extracted with ethyl acetate. After the extract was dried, the solvent was distilled off under reduced pressure to obtain 5.0 g (yield: 77%) of 6-acetyl-2-mercaptobenzoic acid.

Then 6-acetyl-2-mercaptobenzoic acid 5.0
After suspending 6.7 g of 4,6-simethoxy-2-methylsulfonylpyrimidine and 3.5 g of anhydrous potassium carbonate in 20 mQ of dimethyl sulfoxide,
Stir for hours. The reaction solution was poured into a large amount of water and washed with chloroform. The aqueous layer was made acidic by adding concentrated hydrochloric acid, and the resulting oil was extracted with diethyl ether. The diethyl ether layer was washed with water, dried, and then passed through a layer of Florisil to remove impurities. Thereafter, the solvent was distilled off under reduced pressure to obtain the target compound 1. as a pale yellow powder. Ig was obtained.

Melting point: 177-180°C.

Example 2 2-(4,6-cymethoxypyrimidine-2-
Synthesis of ylthio)-6-methylthiobenzoic acid (compound 18) 6-Fluoro-2-methylthiobenzonitrile 16.7
g and 10.4 g of sodium hydrosulfide were suspended in dimethyl sulfoxide roomQ, and the mixture was heated and stirred at 80° C. for 2 hours. After the completion of the reaction, the mixture was poured into a large amount of ice water, the pH of the solution was adjusted to 11-12 using sodium hydroxide, and the neutral components were extracted with chloroform. The aqueous layer was made acidic with concentrated hydrochloric acid, and the resulting oil was extracted with ethyl acetate, washed with water, dried, and the solvent was distilled off to obtain 8.3 g of an oily substance.

Next, an aqueous solution consisting of 6.3 g of oily substance, 8.3 g of sodium sulfide, 7.0 g of sodium hydroxide, and 30 m2 of water was sealed in an autoclave and heated at a liquid temperature of 170 to 180°C and an internal pressure of 8 to 10 kg, 7 cm for 7 hours. After cooling,
The mixture was poured into ice water, the pH was adjusted to 9 to 10, and the mixture was washed with chloroform. The aqueous layer was acidified with concentrated hydrochloric acid, and the resulting oil was extracted with ethyl acetate. After washing the organic layer with water and drying, the solvent was distilled off under reduced pressure to obtain 6.6 g of 6-methylthio-2-mercaptobenzoic acid.

Then 6-methylthio-2-mercaptobenzoic acid 3.
Og, 3.6 g of 4,6-simethoxy-2-methylsulfonylpyrimidine and 2.1 g of sodium hydroxide, N,
It was dissolved in a mixture of N-dimethylformamide 15rnQ and water 10mg, and stirred at room temperature for 3 hours. The reaction solution was poured into a large amount of water and washed with chloroform. The aqueous layer was made acidic by adding concentrated hydrochloric acid, and the resulting oil was extracted with diethyl ether.

The diethyl ether layer was washed with water, dried, and then passed through a layer of Florisil to remove impurities.

Then, the solvent was distilled off under reduced pressure to obtain the target compound 1 as a white powder.
．． 4g was obtained. Melting point 145-147°C.

Example 36 - Synthesis of methyl medoxy 2- (4,6-cymethoxypyrimidin-2-ylthio)benzoate (compound 7) After suspending 0.2 g of % sodium hydride, 6-medoxy 2- (4,6
-cymethoxypyrimidi-2-ylthio)benzoic acid 1.6
g and stirred for 30 minutes. Next, methyl iodide 0.
8 g was added dropwise to the mixture at room temperature, and the mixture was further stirred for 3 hours. The mixture was poured into water and extracted with a mixture of toluene and ethyl acetate. After washing the extract with water and drying, the solvent was distilled off under reduced pressure to obtain 1.4 g of the target compound as a white solid. Melting point 120~
+21'l:.

The herbicide of the present invention contains a pyrimidine derivative represented by the general formula [rl and a salt thereof as an active ingredient.

When the compound of the present invention is used as a herbicide in rice fields, fields, orchards, non-agricultural lands, etc., the active ingredient can be used in an appropriate dosage form depending on the purpose.

In normal cases, the active ingredient is diluted with an inert liquid or solid carrier, and if necessary, surfactants, dispersants, adjuvants, etc. are added to form powders, wettable powders, emulsions, granules, etc. It can be formulated and used in various forms. Examples of carriers used in formulation include solid carriers such as dicrite, talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, urea, 2-propanol, xylene, cyclohexanone, Examples include liquid carriers such as methylnaphthalene.

Examples of surfactants and dispersants include alcohol sulfate salts, alkylaryl sulfonates, lignin sulfonates, polyoxyethylene glycol ethers, polyoxyethylene alkylaryl ethers, and polyoxyethylene sorbitan monoalkylates. .

Examples of adjuvants include carboxymethyl cellulose,
Examples include polyethylene glycol and gum arabic. When using it, dilute it to an appropriate concentration and spray it.
Or apply directly. The compound of the present invention has an active ingredient of 0.0% per lo are. Apply Ig to IKg.

In addition, the compound of the present invention may be used as an insecticide, fungicide, or
It may be used in combination with other herbicides, plant growth regulators, fertilizers, etc.

Next, we will give 11 representative formulation examples! The agent method will be specifically explained. In the following description, "part" means part by weight.

Formulation Example 1 10 parts of wettable powder compound (6), 0.5 part of Emulgen (registered trademark of Kao Corporation) 8IO, 0.5 part of Demol (registered trademark of Kao Corporation) N, Kunilite (Kunimine Kogyo Co., Ltd.) 201 (registered trademark of ZICRITE Co., Ltd.) and 69 parts of ZICRITE CA (registered trademark of ZICRITE Co., Ltd.) are mixed and ground to obtain a wettable powder.

Formulation example 2 Hydrating agent of Emulgen 810 to 10 parts of compound (8). .

5 parts, 0.5 parts of Demol N, 20 of Kunilite 201
Part 5 of Carplex 8o, Part 6 of Zeekrite CA
4 parts were mixed and ground to obtain a wettable powder.

Formulation Example 3 To 30 parts of emulsion compound (15), 60 parts of a mixture of equal amounts of xylene and isophorone and 10 parts of surfactant Tsurupol (registered trademark of Toho Chemical Industry Co., Ltd.) 800A are added, and these are thoroughly stirred to form an emulsion. get.

Formulation Example 4 One part of granule compound (18), one part of talc and one part of bentonite
80 parts of bulking agent mixed in a ratio of 3 parts, 5 parts of white carbon, 5 parts of surfactant Tsurupol 800A and 1 part of water.
Add 0 parts and knead well to make a paste with a diameter of 0.
．． After extruding through a 7mm sieve hole and drying, 0.5
Cut into lengths of ~1 mm to obtain granules.

(Effect of the invention) The compound of the present invention represented by the general formula [+] and its salt are:
Annual weeds that occur in rice fields, such as Japanese grasshopper, Japanese cypress, and Japanese cypress;
It exhibits excellent herbicidal effects at extremely low dosages over a wide range of perennial weeds, such as firefly and grasshopper, from the time of germination to the growing season. In addition, there are various weeds that can be a problem in fields, such as broad-leaved weeds such as Japanese knotweed, Japanese knotweed, whiteweed, chickweed, Japanese chickweed, Japanese goldenrod, morning glory, and Japanese fir tree, as well as perennial weeds such as Japanese knotweed, Japanese yellowtail, Japanese cypress, Japanese cyperus, and Japanese cyperus. It is possible to effectively control grass weeds such as annual Cyperaceae weeds, barnyard grass, grasshopper, foxtail grass, sycamore grass, johnson grass, sycamore grass, and wild oat. On the other hand, the herbicide of the present invention is highly safe for crops, especially rice, wheat, soybeans, cotton, and the like.

Next, the effects of the compounds of the present invention will be explained by giving test examples.

Test example 1 (herbicidal effect test by paddy soil treatment) 100
Fill paddy soil in a plastic pot of 1.5 cm in size, and after puddling, sow seeds of Japanese millet (Ec), Japanese moss (Mo), and bulrush (Sc) at a depth of 0.5 cm, and place the seeds in a water depth of 3 cm.
It was flooded to cm. The next day, the wettable powder prepared according to Formulation Example 1 was diluted with water and dropped onto the water surface. The application amount was 100 g of active ingredient per 10 ares. Thereafter, the plants were grown in a greenhouse, and 28 days after treatment, the herbicidal effect was investigated according to the standards in Table 2. The results are shown in Table 3.

Table 2 Table 3 Table 3 continued Test example 2 (herbicidal effect test by field soil treatment) 120c
+a'' tick pots were filled with upland soil and covered with soil by sowing seeds of Japanese knotweed (Pa), Japanese knotweed (An+), whiteberry (Ch), and blackberry (Ci).

A wettable powder prepared according to Formulation Example 1 was diluted with water, and 100Q per 10 ares was uniformly sprayed on the soil surface using a small sprayer so that the active ingredient was 1 OOg per 10 ares. Thereafter, they were grown in a greenhouse, and 20 days after treatment, the herbicidal effect was investigated according to the standards in Table 2. The results are shown in Table 4.

Table 4 Table 4 Continued Test Example 3 (Reed removal effect test by field soil stem and leaf treatment) 120c
m'' plastic pots were filled with upland soil, and seeds of Japanese knotweed (PO), Japanese violet (Am), white cherries (Ch), and cypress (C1) were sown and covered with soil. After growing in a greenhouse for two weeks, formulation example] The hydrating agent prepared according to the above method was diluted with water, and 100Q per 10 ares was sprayed on the foliage from the top of the plant using a small sprayer so that the active ingredient was 100 g per 10 ares.Then, the greenhouse The herbicidal effect was investigated 14 days after treatment according to the standards in Table 2. The test results are shown in Table 5.

In addition, the following compounds were used as comparative drugs. The same applies to subsequent test examples.

Compound (A) (Compound described in JP-A-62-174059) Shiri.

(Compounds described in JP-A No. 54-55729) Table 5 Test Example 4 (Medical efficacy/toxicity test in field soil treatment) 6
00cm' brass stig pots were each filled with upland soil, and type A cotton (GO), barnyard grass (Ec), johnson grass (SO), Japanese knotweed (Po), and blueberry (
Am), Shiroza (Ch), Noasagao (Ip), and Onamia (Xa) were sown, and tubers of Japanese sedge (Cr) were placed on the bed and covered with soil. Type B also includes soybean (Gl), barnyard grass (Ec), crabgrass (Di), and johnson grass (S).
o), Japanese knotweed (Pa), Japanese knotweed (Am), and white grass (Ch) were sown, and tubers of Japanese knotweed (Cr) were placed on the bed and covered with soil.

After absorbing water from the bottom of the pot, a predetermined amount of the active ingredient of the wettable powder prepared according to Formulation Example 1 was diluted with 10g of water per 10are, and the mixture was sprayed onto the soil surface using a small sprayer. Thereafter, they were grown in a greenhouse, and 20 days after treatment, their herbicidal effects and phytotoxicity were investigated according to the standards in Table 2. The result is the 6th
- Shown in Table A and Table 6-B.

Test Example 5 (Medicinal efficacy/phytotoxicity test by field soil, stem, and leaf treatment) 600
Fill each cm+' plastic pot with upland soil,
Cotton (GO), Japanese barnyard grass (Ec), Johnson grass (So)
, Japanese knotweed (Po), Japanese bluetail (Am), and silverfish (
Ch), Noasagao (Ip), and Onamia (Xa) were sown, and tubers of Red-bellied lily (Cr) were placed on the bed and covered with soil. After absorbing water from the bottom of Bo Soto and growing it in a greenhouse for 2 weeks, a predetermined amount of active ingredient in a hydrating powder prepared according to Formulation Example 1 was added to 10
It was diluted with 100 ρ of water per area and sprayed on the entire plant from above using a small sprayer.

Thereafter, the plants were grown again in the greenhouse, and the herbicidal effect was investigated 14 days after treatment according to the standards in Table 2. The results are shown in the 7th section.
Shown in the table.

Test Example 6 (Crop selectivity test by paddy soil treatment) 1
/ 5000a Wagner pot filled with paddy soil,
After watering and puddling, seeds of Japanese barnyard grass (Ec), Japanese mulberry (Mo), and firefly (Sc) were sown at a depth of 0.5 cm, and the sprouted tubers of Urikawa (Sa) were sown at a depth of 2 cm, two individuals per pot. After burying the soil, two paddy rice plants (Or) at the 2.5-leaf stage were transplanted to a depth of 2 cm and submerged in water to a depth of 3 cm. The next day, a predetermined amount of the active ingredient of a wettable powder prepared according to Preparation Example 1 was diluted with water and dropped onto the water surface. Thereafter, they were grown in a greenhouse, and 28 days after treatment, the herbicidal effect and phytotoxicity were investigated according to the standards in Table 2. The results are shown in Table 8.

Table 8 Ihara Chemical Industry Co., Ltd. Procedural Amendment (white side November 20, 1990 1, Description of the case 1990 Patent Application No. 229259 2, Name of the invention pyrimidine derivatives and herbicides 3, Person making the amendment) Relationship to the incident Patent applicant address: 1-4-26 Ikenohata, Taito-ku, Tokyo Telephone: 03 (
822) 5178 4. Date of amendment order Voluntary action 5. Subject of amendment (1) "Tick pot" in line 9 from the bottom of page 22 of the specification is corrected to "plastic pot."

(2) In Table 6-B on page 22 of the specification " that's all

Claims (2)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, A phenoxyalkoxy group, an alkoxyalkylthio group, an alkyl group, or a phenylthio group optionally substituted with a halogen atom, a pyrrole group, or a cycloalkylalkoxy group, R represents a hydrogen atom, an alkyl group, or a benzyl group, and n is 1 or 2 (wherein, when X represents an alkyl group or a halogen atom, n represents 2.) and salts thereof. (2) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, A phenoxyalkoxy group, an alkoxyalkylthio group, an alkyl group, or a phenylthio group optionally substituted with a halogen atom, a pyrrole group, or a cycloalkylalkoxy group, R represents a hydrogen atom, an alkyl group, or a benzyl group, and n is 1 or 2 (wherein, when X represents an alkyl group or a halogen atom, n represents 2.) A herbicide containing a pyrimidine derivative and its salt as an active ingredient.