JPS63258462A - 2-phenoxypyrimidine derivative and herbicide - Google Patents

Abstract

NEW MATERIAL:The 2-phenoxypyrimidine derivative of formula III [R<1> is H, lower alkyl or benzyl; X is residue of acetylene, pyrrole or dithioacetal or group of formula II (n is 0-2)]. EXAMPLE:2-(4,6-Dimethoxypyridin-2-yl)oxy-6-pyrrolylbenzoic acid. USE:An active component for herbicide. Useful as a herbicide suitable for the treatment of paddy field, plowed land, non-crop land, etc. It exhibits excellent herbicidal effect especially against nut grass and Johnson grass and has high safety to crops. PREPARATION:The objective compound of formula III can be produced e.g. by reacting a compound of formula I with a pyrimidine compound of formula II [R<2> is halogen, alkylsulfonyl or (substituted)benzylsulfonyl] in the presence of a base (e.g. NaHCO3) preferably in a solvent (e.g. dimethylformamide) at a temperature between room temperature and the boiling point of the solvent for 1-24hr.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a novel 2-phenoxypyrimidine derivative and a herbicide containing the same as an active ingredient that can be applied to paddy fields, fields, non-agricultural land, etc. .

(Prior art) The fact that 2-phenoxypyrimidine derivatives have herbicidal activity is known from (1) Agricultural and Biological Chemistry (Agr, Biol, Chem,)
Volume 50, No. 9, Page 896 (1966), (21 JP-A-54-55729- Specification (3)%
-117486 publication specification and (4) Japanese Patent Publication No. 42-
It is described in Publication No. 9474, Specification 1, etc.

(Problems to be Solved by the Invention) However, the control effects of the compounds described in these patent specifications and literature on annual weeds are insufficient;
Moreover, it has the disadvantage of showing almost no activity against perennial weeds.

As a result of intensive research aimed at developing 2-phenoxypyrimidine compounds with excellent herbicidal activity, the present inventors discovered that the present invention compound with substituents introduced into specific positions on the pyrimidine ring and benzene ring has a one-year lifespan. The present invention was completed based on the discovery that the present invention exhibits an excellent herbicidal effect on not only weeds but also perennial weeds, especially mulberry grass and johnson grass, and is extremely safe for crops.

(Means for Solving the Problems) The 2-phenoxypyrimidine derivative of the present invention has the general formula [wherein R1 represents a hydrogen atom, a lower alkyl group, or a benzyl group]. ), and X represents an acetylene group, a pyrrole group, a dithioacetal group, or a group 2. ]. ] The compounds of the present invention represented by the above general formula (1) are illustrated in Table 1.

In addition, the compound number will be referred to in the following description.

〇Table 1 41 The compounds of the present invention can be produced according to the following methods, but are not limited to these methods.

(Method A) (wherein R2 is a halogen atom, an alkylsulfonyl group,
It represents a pencilsulfonyl group or a substituted benzylsulfonyl group, and R1 and X have the same meanings as above. ) Among the compounds of the present invention, the compound represented by formula [6] is represented by formula [1]
] and a pyrimidine compound represented by formula [2] in the presence of a base, preferably in a solvent at a temperature ranging from room temperature to the boiling point of the solvent for 1 to 24 hours.

When carrying out the reaction without a solvent, an alkali metal carbonate such as anhydrous potassium carbonate is used as a base.
It is also possible to carry out the reaction within a temperature range of -160°C.

Examples of the solvent used here include hydrocarbon solvents such as benzene, toluene, and xylene, methylene chloride,
Halogenated hydrocarbon solvents such as chloroform, alcohol solvents such as methanol, ethanol, and isopropanol, ether solvents such as ethyl ether, isopropyl ether, tetrahydrofuran, and 1,4-dioxane,
Examples include ketone solvents such as acetone and methyl ethyl ketone, ester solvents such as methyl acetate and ethyl acetate, aprotic polar solvents such as dimethylformamide, dimethylacetamide, and dimethyl sulfoxide, acetonitrile, and water. 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 carbonated water. Examples include carbonates such as sodium and potassium hydrogen carbonate, and metal hydroxides such as sodium hydroxide and potassium hydroxide.

(Method B) -(4) [5) [6] (In the formula, RB represents a lower alkyl group or a benzyl group, M represents an alkali metal or an alkaline earth metal, and X has the same meaning as above. ) The compound of the present invention represented by formula [6] can be prepared by mixing the compound represented by formula [4] in the presence of a base in a polar solvent, water, or a mixed solvent of a polar solvent and water at room temperature or at the boiling point of the solvent. It can be produced by reacting at a temperature range of 0.5 to 66 hours to produce a compound represented by formula 7 [5], and then precipitating this compound with acid.

Examples of the solvent used here include alcohol solvents such as methanol, ethanol, and isopropanol, and ketone solvents such as acetone and methyl ethyl ketone. In addition, as a base, for example, sodium carbonate,
potassium carbonate, calcium carbonate, sodium bicarbonate,
Examples include carbonates such as potassium hydrogen carbonate, and metal hydroxides such as sodium hydroxide and potassium hydroxide.

Furthermore, when R4 in [4] represents a benzyl group,
Formula [6] can also be produced by a catalytic reduction method using hydrogen.

Next, an example will be given and explained.

Example 1 Synthesis of benzyl 2-C4,6-cymethoxypyridin-2-yl)oxy-6-pyrrolylbenzoate (compound 7) Benzyl 6-pyrrolylsalicylate (4,2y-), 4.
6-Simethoxy2-methylsulfonylpyrimidine (3
,4j? ) and potassium hydrogen carbonate (1,7y-) in dimethylformamide (20m), 100-110
The mixture was heated and stirred at ℃ for 1 hour. After cooling, the reaction solution was poured into water.
Extracted with ethyl acetate. After washing the extract with water and drying, the solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography to obtain the title compound as a white amorphous solid (3,3y-).

(Melting point 111-116°C) Example 2 Synthesis of 2-C4,6-simethoxypyridin-2-yl)oxy-6-pyrrolylbenzoic acid (Compound 8) 10 polypalladium thiacol (0,5,@), Methyl alcohol (
After suspending ethyl acetate (50 mt) and acetic acid (20 mt), 2-(4,6-cymethoxypyridine-2
-yl)oxy-6-pyrrolylbenzoate benzyl (2,
3!1I-) was added to perform catalytic reduction under normal pressure. When hydrogen absorption ceased, the catalyst was filtered off, and the filtrate was concentrated.

The residue was dissolved in ethyl acetate, washed with water, dried, and then the solvent was distilled off under reduced pressure to give the title compound as white crystals (i, 1, P).
The herbicide of the present invention contains a 2-phenoxypyrimidine derivative, which is a compound of the present invention.

When the compound of the present invention is used as a herbicide, a carrier, a surfactant, a dispersant, an auxiliary agent, etc., which are commonly used in the formulation of agricultural chemicals, are blended with the compound or with the compound to form a hydrating agent. It can be formulated and used in various forms such as granules, emulsions, or powders.

Examples of carriers used in formulation 2 include dicrite, talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermicelliite, slaked lime, silica sand, ammonium sulfate, urea and other surrounding carriers, isopropyl alcohol, Examples include liquid carriers such as xylene, cyclohexane, and methylnaphthalene. Examples of surfactants and dispersants include alcohol sulfate ester salt, alkylaryl sulfonate, lignin sulfonate, polyoxyethylene glycol ether, polyoxyethylene argylaryl ether, polyoxyethylene sorbitan monoalkyl 1/ - etc. Examples of the adjuvant 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.

Moreover, the herbicide of the present invention can also be used in combination with other herbicides.

The herbicide of the present invention can control various weeds that occur in rice fields by treating the soil with water or treating the foliage before or after the germination of the weeds. In addition, various weeds occurring in fields can be controlled by treating the soil or treating the foliage before or after the germination of the weeds.

The herbicide of the present invention has an active ingredient of 0 to 1 per 10 ares.
9 applications to f~1. Also, when spraying on plant stems and leaves,
It is applied diluted to between ppm and j 0000 ppm.

Next, Examples of the herbicide of the present invention will be given, but the present invention is not limited to this range.

In addition, φ described in the examples indicates weight percentage.

Example 3 (Wettable powder) Compound (7) 10%, Emulgen 810 (registered trademark of Kao Soap Co., Ltd.) 11. sg&, Demol N (registered trademark of Kao Soap Co., Ltd.) 0.51+, Kunilite (registered trademark of Kunimine Industries Co., Ltd.) 201 20'%, and Zikrite (registered trademark of Zikrite Co., Ltd.) CA69% are uniformly mixed and ground. It was used as a hydrating agent.

Example 4 (Emulsion) Compounds (113096, 20% cyclohexanone, 11% polyoxyethylene alkylaryl ether, 49% calcium alkylbenzenesulfonate, and 65% methylnaphthalene) were uniformly dissolved to prepare an emulsion.

Example 5 (granules) Compound (9) 5%, sodium salt of lauryl alcohol sulfate 2%, sodium lignin sulfonate 5%, carboxymethyl cellulose 2, and clay 8
Mix and grind 6% uniformly. 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 6 (Powder) 2% of compound (8), ±5 diatoms, and 93% of clay were uniformly mixed and ground to obtain a powder.

(Effects of the Invention) The compounds and herbicides of the present invention can effectively control annual weeds that occur in rice fields, such as Japanese grasshopper, Japanese cypress, Japanese cypress, Japanese cypress, Japanese cypress, and perennial weeds such as Japanese cypress, Japanese cypress, and black cypress. Also,
Japanese barnyard grass, crabgrass, black-and-white grass, foxtail grass, sycamore, sycamore, oat, Italian ryegrass, Japanese knotweed, blueberry, whiteweed, redweed, Japanese croaker, golden deer, yellowtail grass, chickweed, morning glory, Japanese fir, Japanese snail, Japanese snail, and itch. It is also possible to effectively control annual weeds such as grass, grass, buckwheat, wild mustard, and helium, as well as perennial weeds such as common grass, johnson grass, silver grass, and grasshopper. On the other hand, it is extremely safe for crops. Furthermore,
Toward the Present Invention The compound is characterized in that it has an excellent herbicidal effect on perennial weeds such as sedges as well as hand weeds, even when compared with the known compounds described in the above-mentioned literature.

Next, the effects of the herbicide of the present invention will be explained using test examples.

Test Example 1 (Treatment of Stalks and Leaves) Seeds of Japanese barnyard grass, Japanese knotweed, Japanese knotweed, Japanese violet, white-tailed grass, and Japanese cypress were sown in a 100 m pot filled with soil, and covered with soil at a concentration of 0.5 to 1 cr/L. After growing the pot in a glass room at 20 to 25°C for two weeks, add a hydrating powder prepared according to Example B to the active ingredient at 40% per 10 ares.
Dilute with 100 tons of water per 10 are so that it becomes 0.
Sprayed on the surface of the leaves. The survey was carried out 1 and 2 times on the 14th day after drug treatment.
It was conducted according to the standards in the table. The results are shown in Table 6 as an index.

Table 2 Table 6 (note) t The abbreviations for test plants represent the following plants.

(The same applies to other tables) Ech; Millet (Echinochlo)
a crus-gali) Dig;
(Digitalia adscendens)Po
l; Polygonum nod
osum) Ama; Aobiyu (Amaran)
thus retroflexus) Che; Shiroza (Chenopodium album)
Cyi; Cyperus 1r
ia) 2. Comparative compounds A, B and C represent the following compounds. (Other tables are the same) Biol, Chem,) Volume 30, 9
No., p. 896 (1966) Test Example 2 (Soil treatment) Seeds of Japanese barnyard grass, Japanese knotweed, Japanese knotweed, Japanese violet, white-tailed grass, and Japanese cypress were sown in a 1-oad pot filled with soil, and the seeds were covered with soil to a depth of 0.5 to 1 cfIL. On the day after sowing, a hydrating agent prepared according to Example B was diluted with the active ingredient to a concentration of 400/10 ares with 100 tons of water per 10 ares, and was sprayed on the soil surface. The results of the investigation conducted on the 20th day of drug treatment according to the criteria in Table 2 are shown in Table 4 as an index.

Table 4 Test Example 3 (Effect on perennial weeds) Covering the tubers of the common grass in a 60 oc11t bot filled with soil.
．． 5 to 1 were embedded to a thickness of . In the soil treatment, one day after sowing, a predetermined amount of the aqueous phase agent prepared according to Example 3 was diluted with 100 tons of water per 10 ares and sprayed on the soil surface.

In addition, in the foliage treatment, after growing the pots in a glass room at 20 to 25°C for two weeks, a predetermined amount of a hydrating powder prepared according to Example 4 was used as a spreading agent and surfactant WK 20 was used.
The solution was diluted with 100 tons of water per 10 are containing a concentration of 0.00 ppm and sprayed on the surfaces of the leaves.

The survey was conducted on the 50th day of chemical treatment for soil treatment, and on the 2nd day for foliage treatment.
I went on the first day. The results are indexed according to the criteria in Table 2.
Shown in the table.

Table 5 (note) Comparative compounds represent the following compounds.

r

Claims (2)

[Claims] (1) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R^1 represents a hydrogen atom, a lower alkyl group, or a benzyl group. ), and X is an acetylene group, pyrrole group, dithioacetal group, or group ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, n is 0, 1
, or 2. ) is shown. ] A 2-phenoxypyrimidine derivative represented by: (2) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R^1 represents a hydrogen atom, a lower alkyl group, or a benzyl group. ), and X is an acetylene group, pyrrole group, dithioacetal group, or group ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, n is 0, 1
, or 2. ) is shown. ] A herbicide containing a 2-phenoxypyrimidine derivative represented by the following as an active ingredient.