JPH0217187A - Phenoxypropionamide derivative and herbicide - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [R is H or halogen; X is O or S; Y is 5- to 6-membered heterocyclic ring which may contain 1-3 N atoms or 1 S atom (the ring may be substituted by 1-2 O, halogen, lower alkyl, lower alkoxy or lower alkylamino)] and salts thereof. EXAMPLE:N-(2, 5-Dimethyl-3-pyrazolyl)-2-[4-(4-chlorobenzoxazolyl-2-oxy) phenoxy] propionamide. USE:A herbicide capable of exhibiting excellent herbicidal effects on gramineous weeds. PREPARATION:A compound expressed by formula II is reacted with a compound expressed by formula III (Z is halogen, alkylsulfonyl or benzenesulfonyl) in the presence of a base, such as sodium hydroxide or triethylamine, preferably at 50-100 deg.C for 1-6hr.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel phenoxypropionic acid amide derivative and a herbicide containing the same as an active ingredient.

2. Prior Art It has been known that certain phenoxypropionic acid amide derivatives have herbicidal activity (Patent H.
IG767% public $11, special publication number H 54-11208).

However, these compounds do not necessarily have a high herbicidal effect on weeds of the grass family such as barnyard grass, foxtail grass, and quince grass, and are not necessarily safe for useful crops such as rice and wheat, which poses practical problems.

Problems to be Solved by the Invention The present invention overcomes the problems of conventional phenoxypropionic acid amide derivatives and provides a novel phenoxypropionic acid that has both an excellent herbicidal effect on weeds of the family Weeds and a high degree of safety for useful crops. This was done for the purpose of providing amide derivatives.

Means for Solving the Problems The present inventors have conducted extensive research with the aim of developing such improved phenoxypropionic acid amide compounds.
As a result, it was discovered that the compound of the present invention exhibits an excellent herbicidal effect against grasshopper weeds such as barnyard grass, jack grass, foxtail grass, and quince grass, and is highly safe for useful crops, particularly wheat and rice, and the present invention I was able to complete it.

That is, the present invention is exemplified by the following general formula (I). Compound numbers are referred to in the following description.

[In the formula, R represents a hydrogen atom or a halogen atom, X represents an oxygen atom or a sulfur atom, and Y represents 1 to 3 nitrogen atoms.
may contain 1 sulfur atom, 5 to 6
A phenoxypropionic acid amide derivative represented by a membered heterocycle (the linear ring may be substituted with 1 or 2 oxygen atoms, a halogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkylamino group) and its salts.

The compounds of the present invention represented by the above general formula are shown in Table 1, and infrared absorption spectra of compounds in Table 1 that cannot be measured are shown in Figs. 1 to 10, respectively.

The compound of the present invention can be produced by the method shown in Reaction Formula (1) and Reaction Formula (2). However, the method is not limited to these methods.

Reaction formula (1) (In the formula, Z represents a halogen atom, an alkylsulfonyl group, or a benzenesulfonyl group, and R, X and Y have the same meanings as above.) As shown in the reaction formula (L), - formula The compound of the present invention represented by general formula (I) can be produced by reacting the compound represented by (II) with the compound represented by formula CIII) in the presence of a base.

Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, sodium carbonate,
Inorganic bases such as alkali metal carbonates such as potassium carbonate, alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, or triethylamine, N,N-dimethylaniline, pyridine, I,8-diazabicyclo[5
, 4, O3 unde-7-cene and the like.

In addition, if necessary, tetra-n-butylammonium bromide, 1 Tocro-6 (1,4,7,10,
By adding a phase transfer catalyst such as 1316-hexaoxacyclooctadecane), the desired reaction can be carried out quickly.

The reaction can be carried out in the presence of one or more suitable diluents, if necessary. The diluent is an inert organic solvent, such as ketones such as acetone and butanone, aromatic hydrocarbons such as benzene, tonolenine, xylene, and chlorobenzene, aliphatic hydrocarbons such as petroleum ether and ligroin, diethyl ether, tetrahydro 7
Ran, ethers such as dioxane, acetonitrile Ju,
Examples include nitriles such as propionitrile, and amides such as N,N-dimethylformamide, N,todimethylacetamide, and tomethylpyrrolidone.

The reaction temperature is usually any value from 0°C to the reflux temperature of the reaction system, preferably from 50°C to 100°C.The reaction time varies depending on the compound, but usually a reaction time of 1 to 6 hours will give a good yield. You can get what you want.

Reaction formula (2) (wherein, R, X, Y and Z have the same meanings as above) As shown in reaction formula (2), a compound represented by general formula (IV) and general formula (V) The compound of the present invention represented by general formula (I) can also be produced by reacting the compound represented by formula (I) with the compound represented by formula (I) in the presence of a base.

Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, sodium carbonate,
Alkali metal carbonates such as potassium carbonate, inorganic bases such as alkali gold bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, or triethylamine, H, triethylamine, pyridine, 1. Tojiazabicyclo[5,LO
Examples include organic bases such as I unde-7-cene.

In addition, if necessary, tetra-n-butylammonium bromide, 1 Tocro-6 (+, 4, 7.10.1
By adding a phase transfer catalyst such as 3.16-hexaoxanechlorooctadecane), the desired reaction can be carried out quickly.

The reaction can be carried out in the presence of one or more suitable diluents, if necessary. The diluent is an inert organic solvent, such as ketones such as acetone and butanone, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene, aliphatic hydrocarbons such as petroleum ether and ligroin, Examples include ethers such as diethyl ether, tetrahydrofuran and dioxane, nitriles such as acetonitrile and propionitrile, and amides such as N,N-dimethylformamide, N,N-dimethylacetamide and tomethylpyrrolidone.

The reaction temperature is generally any value from 0°C to the reflux temperature in the reaction system, preferably 50°C to IH°C. Although the reaction time varies depending on the compound, the desired product can be obtained in good yield if the reaction is generally carried out for 1 to 6 hours.

EXAMPLES Next, the present invention will be explained in more detail by examples.
The present invention is not limited to the following examples unless it exceeds the gist thereof.

Example 1 N-(L5-dimethyl-3-pyrazolyl)-2-[+
-(6-thalolopenzoxazolyl-2-oxy)phenoxy] Production of propionic acid amide (compound number +9) (-(6-chloropenzoxazolyl-2-oxy)phenol 1.Sy (5,7 mmol), N-(L
To a solution consisting of 1.49 (5.7 mmol) of 5-dimethyltovirazolyl)-tobromoprobionic acid amide and 1 ml of acetonitrile was added 0.99 (6,0 ml) of potassium carbonate.
5 mmol) and a catalytic amount of tetra-n-butylammonium bromide were added, and the mixture was stirred under heating under reflux for 3 hours.

After the reaction was completed, it was cooled to room temperature, the solid was filtered off, the solvent was distilled off under reduced pressure, and the resulting residue was purified by column chromatography to obtain 2.0 g of the target product (yield: 8
3%, melting point ■1~l45'C)? ! 4f:.

Example 2 N-(1,6-dimethyltopyridyl)-2-(4-
Preparation of (6-talolopenzoxazolyl-2-oxy)phenoxy]propionic acid amide (Compound No. 6)2.
6-dichlorobenzoxazole 1.19 (5.9 mmol), N-(4j-dimethyl-tobiridyl)-t(
4-Hydroxyphenoxy)propionic acid amide 1. Lid (s, 1 mmol) and acetonitrile lO1110
1.09 (7.2 mmol) of potassium carbonate and a catalytic amount of tetra-n-butylammonium bromide were added to a solution consisting of 1 liter, and the mixture was stirred under heating under reflux for 3 hours.

After the reaction was completed, the desired product 139 (yield 88%, melting point 93-94°C) was obtained by processing in the same manner as in Example 1.

Example 3 To(≦-chloroviridyl') -2-[4-(6-
Preparation of chloropenzothiazolyl-2-oxy)phenoxy J propionic acid amide (compound no. 25) 2.6-dichlorobenzothiazole l-5y (7.4 mmol),
N-(S-chloro-2-pyridyl)-2-(4-hydroxyphenoxy)propionic acid amide 129 (7.5 mmol) and N,11-dimethylformamide 100 m
1.2y (1.7 mmol) of potassium carbonate was added to the solution consisting of 1, and the mixture was stirred at 100°C for 3 hours.

After the reaction was completed, the desired product 3.09 (yield 88%, melting point 111-115°C) was obtained by processing in the same manner as in Example 1.
I got it.

The herbicide of the present invention contains the compound of the present invention, a phenoxypropionic acid amide derivative, as an active ingredient.

When the compound of the present invention is used as a herbicide, the compound alone or the compound commonly used in the formulation of agricultural chemicals,
It can be formulated into various forms such as wettable powders, granules, emulsions, or powders by adding carriers, surfactants, dispersants, adjuvants, etc., and used.

Examples of carriers used in formulation include di-
Examples include solid carriers such as clite, talc, bentonite, clay kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, and urea, and liquid carriers W such as inglobil alcohol, xylene, cyclohexane, and methylnaphthalene. Examples of surfactants and dispersants include alcohol sulfate salts, alkylaryl sulfonates, lignin sulfonates, polyoxyethylene glycol ethers, polyoxyethylene alkylaryl ethers, and polyoxyethylene rubitan monoalkylates. I get vignetted. As an adjuvant,
Examples include carboxymethylcellulose, polyethylene glycol, gum arabic, and the like. When using it, either dilute it to an appropriate concentration and spray it, or apply it directly.

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

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

In addition, % described in an example shows a weight percentage.

Example 4 (hydrating powder) Compound (4) 10%, Emulgen 810 (registered trademark of Kao Corporation) O, S%, Demol N (registered trademark of Kao Corporation) G, S%, Kunilite (Kunimi Fu Kogyo Co., Ltd.) Registered trademark)'! 0120% and Zikrite (Zikrite Co., Ltd. registered trademark) CA69% were uniformly mixed and ground to prepare a wettable powder.

Example 5 (Emulsion) An emulsion was prepared by uniformly dissolving 30% of compound (4), 20% of cyclohexanone, 11% of polyoxyethylene alkylaryl ether, 4% of calcium alkylbenzene sulfonate, and 35% of methylnaphthalene.

Example 6 (granules) Compound (4) 5%, sodium salt of lauryl alcohol miminister 2%, sodium lignin sulfonate 5%
, carboquine methylcellulose 2%, and clay 86%
Mix and grind evenly. This mixture +00I! Add 20,111 parts of water to the volume, mix, and use an extrusion granulator to make 1
The mixture was processed into 4 to 32 mesh granules and then dried to form granules.

Example 7 (powder) Compound (4) 2%, diatomaceous earth 5%, and clay 93%
The mixture was uniformly mixed and pulverized to form a powder.

The herbicide of the present invention can control many weeds that occur in upland fields by soil-filtering or foliage-filtering before or after the germination of 11 seeds. In addition, in paddy fields, water EB1. : Many weeds that occur can be controlled.

The agent of the present invention is an active ingredient with a, l per lO are.
Apply y~1&9, preferably 19-4009. Also, when spraying on plant stems and leaves, 1 ppm-110000p
Apply diluted to p.

Effects of the Invention The compounds and herbicides of the present invention can be used to control barnyard grass, black grass, blackgrass, black grass, foxtail grass, etc. that occur in fields.
It is possible to effectively control grasses belonging to the family Hematinaceae, such as johnson grass.

In addition, barnyard grasses that occur in rice fields can also be effectively controlled. On the other hand, it is highly safe for crops, especially wheat and rice.

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

In the following tests, the abbreviations in the table represent the following plants.

Ec; Japanese barnyard grass, Di: Japanese barnyard grass, Se; Japanese foxtail grass, S
Auto: Johnson grass, Or: Rice, T: Wheat Also, the comparative drugs are the following compounds described in JP-A No. 53-40761 Test Example 1 Barnyard grass, Mexican grass, foxtail grass, and Johnson grass were placed in a 600C11" pot filled with soil. Seeds of grass, rice, and wheat were sown and covered with soil in O, S to 1c+++. After the pots were grown 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 diluted with 1 mouth water per 1 #are and sprayed on the foliage surface. The v4 test was conducted 14 days after drug treatment according to the criteria in Table 2. The results are shown in Table 3 as an index.

Test example 2 (paddy field weed control effect) Paddy soil was filled into a 100 cm pot, and after watering and puddling, millet seeds were sown, paddy rice seedlings at the 2-leaf stage were transplanted, and 3c
m1: Flooded with water. On the day after seeding, a predetermined amount of a wettable powder prepared according to Example 4 was diluted with water and dropped onto the water surface. The investigation was conducted 21 days after drug treatment according to the criteria in Table 2. The survey results are shown in Table 4 as an index.

Test Example 3 (Paddy field weed control effect) A 100 cm' pot was filled with paddy soil, and after watering and puddling, barnyard grass seeds were sown, and the pot was flooded at 3c11. 3 barnyard grass
When it reached the leaf stage, it was prepared according to Example 4; a predetermined amount of an irrigation agent was diluted with water and dropped onto the water surface. The investigation was conducted 30 days after drug treatment according to the criteria in Table 2. 5th survey results
It is shown in the table as an index.

[Brief explanation of the drawing]

Figure 1 is an infrared absorption spectrum diagram of compound 11, Figure 2 is an infrared absorption spectrum diagram of compound 12, and Figure 3 is an infrared absorption spectrum diagram of compound 1.
Figure 4 is an infrared absorption spectrum diagram of Compound 15, Figure 5 is an infrared absorption spectrum diagram of Compound 18, No. 6rXJ is an infrared absorption spectrum diagram of Compound 22, and Figure 7 is an infrared absorption spectrum diagram of Compound 22. FIG. 8 is an infrared absorption spectrum diagram of compound 26, FIG. 9 is an infrared absorption spectrum diagram of compound 2B, and FIG. 10 is an infrared absorption spectrum diagram of compound 2.
9 is an infrared absorption spectrum diagram of No. 9.

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R represents a hydrogen atom or a halogen atom, X represents an oxygen atom or a sulfur atom, and Y represents one or more nitrogen atoms. 3
may contain 1 sulfur atom, 5 to 6
a phenoxypropionic acid amide derivative represented by: That salt. 2 The heterocycle is a pyridine ring (the ring may be substituted with 1 or 2 halogen atoms, a lower alkyl group or a lower alkoxy group), a pyrimidine ring (the ring is substituted with 1 or 2 oxygen atoms, a halogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkylamino group), a pyrazole ring (the ring may be substituted with a lower alkyl group), a triazine ring (the ring may be substituted with a lower alkyl group) The phenoxypropionic acid amide derivative and its salt according to claim 1, which is a thiazole ring (the ring may be substituted with a halogen atom) or a thiazole ring (the ring may be substituted with a halogen atom). 3 General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R represents a hydrogen atom or a halogen atom, X represents an oxygen atom or a sulfur atom, and Y represents 1 to 3 nitrogen atoms.
may contain 1 sulfur atom, 5 to 6
a phenoxypropionic acid amide derivative represented by: A herbicide containing the salt as an active ingredient. 4 The heterocycle is a pyridine ring (the ring may be substituted with 1 or 2 halogen atoms, a lower alkyl group or a lower alkoxy group), a pyrimidine ring (the ring is substituted with 1 or 2 oxygen atoms, a halogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkylamino group), a pyrazole ring (the ring may be substituted with a lower alkyl group), a triazine ring (the ring may be substituted with a lower alkyl group) 2. A herbicide containing the phenoxypropionic acid amide derivative and its salt as an active ingredient according to claim 1, which is a thiazole ring (the ring may be substituted with a halogen atom) or a thiazole ring (the ring may be substituted with a halogen atom).