JP2985415B2 - Benzofuran derivative, method for producing the same, herbicide containing the same as an active ingredient, and intermediates thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel benzofuran derivative, a method for producing the same, a herbicide containing the same as an active ingredient, and an intermediate thereof.

[0002]

2. Description of the Related Art Japanese Patent Application Laid-Open No. 48-92533 discloses that a certain kind of substituted uracil is used as an active ingredient of a herbicide. Further, JP-A-63-156787 and the like describe that certain substituted benzofurans are used as active ingredients of herbicides.

[0003]

However, these compounds are not always satisfactory because of their insufficient herbicidal activity and poor selectivity between crops and weeds.

[0004]

Means for Solving the Problems In view of such circumstances, the present inventors have made various studies and as a result, it has been found that certain benzofuran derivatives having a uracil group are compounds having an excellent herbicidal effect with few defects as described above. And reached the present invention.

That is, the present invention provides a compound represented by the following general formula:

Embedded image [Wherein, R represents a lower alkyl group, A represents a hydrogen atom,
X represents an oxygen atom or a sulfur atom, Y represents a hydrogen atom, a fluorine atom, a chlorine atom or a bromine atom, and Z represents a methyl group or an amino group. (Hereinafter, referred to as the compound of the present invention).

Next, a method for producing the compound of the present invention will be described. The compound of the present invention has the general formula

Embedded image [Wherein, R, A, X and Y represent the same meaning as described above. And a compound represented by the general formula:

Embedded image CH ₃ —E wherein E represents a chlorine atom, a bromine atom, an iodine atom or a methanesulfonyloxy group. Or a compound represented by the general formula:

Embedded image NH ₂ -G wherein G represents a methanesulfonyloxy group, a p-toluenesulfonyloxy group or a 2,4-dinitrophenoxy group. And a compound represented by the following formula:

This reaction is usually carried out in a solvent in the presence of a base, the reaction temperature is in the range of 0 to 100 ° C., and the reaction time is in the range of 0.5 to 10 hours. The amount of the compound is as follows:
Alternatively, the compound represented by Chemical formula 1 is 1 to 10 equivalents, and the base is 1 to 1.5 equivalents.

Examples of the solvent include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as chloroform and carbon tetrachloride, diethyl ether, dioxane and tetrahydrofuran. Ethers, such as acetone, methyl isobutyl ketone, etc .; esters, such as ethyl acetate; amides, such as N, N-dimethylformamide; sulfur compounds, such as dimethyl sulfoxide; and mixtures thereof. Examples of the base include inorganic bases such as sodium hydride and potassium hydride, and alkali metal alkoxides such as sodium ethoxide and sodium methoxide.

After completion of the reaction, the reaction solution is poured into water, and the resulting crystals are subjected to ordinary post-treatments such as filtration or extraction with an organic solvent and concentration, and if necessary, purification by operations such as chromatography and recrystallization. Thus, the desired compound of the present invention can be obtained.

The compound of the present invention has the general formula

Embedded image Wherein R ′ and R ″ are the same or different from each other;
Represents a hydrogen atom or a lower alkyl group, and A, X, Y and Z have the same meanings as described above. To the compound of the formula (1) in the presence of a base.

This reaction is usually carried out in a solvent, and the reaction temperature ranges from 20 to 200 ° C., preferably from 60 to 150 ° C.
And the range of the reaction time is 1 to 96 hours. Examples of the base include inorganic bases such as potassium carbonate, potassium fluoride, and cesium fluoride; organic bases such as quaternary ammonium fluoride; and alkali metal alkoxides such as sodium methoxide and sodium ethoxide. The base is used in an amount of 0.1 to 1 equivalent based on 1 equivalent of the compound.

Examples of the solvent include aromatic hydrocarbons such as toluene, xylene and mesitylene, ethers such as 1,4-dioxane and tetrahydrofuran, acid amides such as dimethylformamide, and sulfur compounds such as dimethylsulfoxide and sulfolane. .

After completion of the reaction, the reaction solution is poured into a dilute acid, and the resulting crystals are subjected to ordinary post-treatments such as filtration or extraction with an organic solvent, drying, concentration and the like, and if necessary, purification by recrystallization, chromatography or the like. Thus, the desired compound of the present invention can be obtained.

The compound represented by Chemical Formula 11, which is a starting compound of the above-mentioned production method, is disclosed in JP-A-63-107967 and EP
It can be produced by the method described in JP-A-408382A2.

Further, the compound represented by Chemical formula 8 can be produced according to the route represented by Chemical formula 12.

[0016]

Embedded image

Wherein R, R ′, R ″, A, X and Y
Represents the same meaning as described above. The above reaction is described in detail below.

Method for producing compound [I] → compound [II] Compound [II] can be prepared by reacting compound [I] without solvent or in a solvent.
200 to 300 ° C, preferably 150 to 250 ° C.
It can be manufactured by heating for １００100 hours. As the solvent, toluene, xylene, mesitylene,
Examples include aromatic hydrocarbons such as tetralin, tertiary amines such as diethylaniline, and the like, and mixtures thereof.

After completion of the reaction, the reaction solution is subjected to usual post-treatments such as extraction with an organic solvent and concentration, and if necessary, purification by chromatography, distillation, recrystallization and the like to obtain the desired compound [II]. be able to.

The compound [I] can be obtained from its corresponding phenol derivative or thiophenol derivative by the method described in EP61741.
It can be produced according to the method described in JP-B.

Method for producing compound [II] → compound [III] Compound [III] can be produced by reacting compound [II] in the presence of an acid. This reaction is carried out without solvent or in a solvent, and the reaction temperature ranges from 0 to 10
0 ° C., preferably 5-80 ° C., and the reaction time range is
The reaction is performed for 0.5 to 24 hours, and the amount of the reagent used for the reaction is 1.1 to 100 equivalents of the acid based on 1 equivalent of the compound [II].

Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid and polyphosphoric acid, sulfonic acids such as p-toluenesulfonic acid and trifluoromethanesulfonic acid, and carboxylic acids such as formic acid, acetic acid and trifluoroacetic acid. Examples of the solvent include aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as chloroform and carbon tetrachloride, inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as acetic acid, water and the like, and mixtures thereof. Can be

After completion of the reaction, the reaction mixture is poured into water, and the resulting crystals are subjected to ordinary post-treatments such as filtration or extraction with an organic solvent and concentration, and if necessary, purification by operations such as chromatography, distillation and recrystallization. As a result, the target compound [III] can be obtained.

Method for producing compound [III] → compound [IV] Compound [IV] can be produced by reacting compound [III] with methyl chlorocarbonate. This reaction is usually performed in a solvent in the presence of a base, the reaction temperature is in the range of 0 to 120 ° C, preferably 20 to 80 ° C, and the reaction time is in the range of 0.5 to 5 hours. The amounts of the reagents used in the reaction are 1 to 2 equivalents of methyl chlorocarbonate and 1 to 1.5 equivalents of the base relative to 1 equivalent of the compound [III].

Examples of the base include organic bases such as triethylamine, pyridine and diethylaniline, and inorganic bases such as potassium carbonate and sodium hydride. Examples of the solvent include aromatic hydrocarbons such as benzene and toluene; halogenated hydrocarbons such as chloroform and carbon tetrachloride; ethers such as diethyl ether, dioxane and tetrahydrofuran; ketones such as acetone and methyl isobutyl ketone; And amides such as N-dimethylformamide; sulfur compounds such as dimethylsulfoxide; and mixtures thereof.

After completion of the reaction, the reaction mixture is poured into water, and the resulting crystals are subjected to ordinary post-treatments such as filtration or extraction with an organic solvent and concentration, and, if necessary, purification by operations such as chromatography and recrystallization. The target compound [IV] can be obtained.

Method for producing compound [III] → compound [V] Compound [V] can be produced by reacting compound [I] with phosgene. This reaction is usually
The reaction is carried out in a solvent, the reaction temperature is in the range of 0 to 120 ° C, preferably 20 to 100 ° C, and the reaction time is in the range of 0.5.
Phosgene is used in an amount of 2 to 10 equivalents with respect to 1 equivalent of the compound [III].

Examples of the solvent include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as chloroform and carbon tetrachloride, and mixtures thereof.

After completion of the reaction, the solvent and excess phosgene are distilled off from the reaction solution, and if necessary, the target compound [V] can be obtained by purification by distillation, recrystallization or the like.

Compound [IV] → Method for producing compound of formula 8 The compound of formula 8 is a compound of formula [IV]

Embedded image It can be produced by reacting a compound represented by CF ₃ (NH ₂ ) C ＝ CHCO ₂ C ₂ H ₅ . This reaction is generally carried out in a solvent in the presence of a base, the reaction temperature is in the range of 0 to 150 ° C, preferably 80 to 120 ° C, and the reaction time is in the range of 0.5 to 10 ° C.
Time, and the amount of the reagent used in the reaction is the amount of compound [IV] 1
1 to 10 equivalents of the compound represented by the formula
The base is 1 to 10 equivalents.

Examples of the base include potassium hydride, sodium hydride and the like. Examples of the solvent include aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as benzene and toluene; ethers such as diethyl ether, dioxane and tetrahydrofuran; amides such as N, N-dimethylformamide; and dimethyl sulfoxide. And mixtures thereof.

After completion of the reaction, the reaction mixture is poured into a dilute acid or water, and the resulting crystals are subjected to ordinary post-treatments such as filtration or extraction with an organic solvent and concentration. If necessary, operations such as chromatography, distillation and recrystallization are performed. By purifying the compound by the above method, the desired compound represented by Chemical formula 8 can be obtained.

Compound [V] → Method for producing compound represented by formula 8 The compound represented by formula 8 can also be produced by reacting compound [V] with a compound represented by formula 13. This reaction is generally performed in a solvent in the presence of a base, and the reaction temperature is in a range of 0 to 60 ° C, preferably 5 to 3 ° C.
0 ° C., the reaction time was 0.5 to 10 hours, and the amount of the reagent used for the reaction was 1 equivalent of the compound [V].
Is 1 to 1.5 equivalents, and the base is 1 to 1.5 equivalents.

Examples of the base include sodium hydride, potassium hydride and the like. Examples of the solvent include aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as benzene and toluene; ethers such as diethyl ether, dioxane and tetrahydrofuran; amides such as N, N-dimethylformamide; and dimethyl sulfoxide. And the like, or a mixture thereof.

After the completion of the reaction, the reaction solution is poured into a dilute acid or water, and the resulting crystals are subjected to ordinary post-treatments such as filtration or extraction with an organic solvent and concentration. If necessary, operations such as chromatography, distillation and recrystallization are performed. Thus, the desired compound represented by Chemical formula 8 can be obtained.

In general, the compound of the present invention can be produced by directly using the compound of the formula (I) obtained in the above reaction in the next step without isolation.

The compound of the present invention has an excellent herbicidal effect. That is, the compound of the present invention has an excellent herbicidal effect on various weeds which are problematic in foliage treatment and soil treatment in upland fields.

The weeds that can be controlled by the compound of the present invention include, for example, buckwheat,
Hakobe, Shiroza, Aogatoi, Japanese radish, Japanese agaricus, Nazuna, Acacia catechu, Ebisugusa, Ichibi, Acacia sika, Field pansy, Yaegura, Asakagaa, Albaasagao, Acacia sylvestris, A. Broadleaf weeds, such as corn fir, sunflower, dog chamomile, corn marigold, spurge, oenix alga, barnyard grass, barnyardgrass, enokorogosa, mehisiba, spruce anemone, nossinopepo, oats, oats, scorpiones, anemones Weeds and Cyperaceae weeds such as communis, Cyperaceae weeds, Cyperaceae weeds such as Lepidoptera It has a herbicidal effect for, moreover,
Some of the compounds of the present invention include corn, wheat,
It does not show any phytotoxicity that could cause problems for major crops such as rice, soybean, and cotton.

Some of the compounds of the present invention include various weeds which are problematic in flooding treatment of paddy fields, for example, grass weeds such as sand flies, broadleaf weeds such as azena, kikasigusa, mizohakobe, tamayatsuri, firefly, It has a herbicidal effect on cyperaceae weeds such as pine fever and horned vine, such as weeds, oak and urikawa, and does not show any harmful harm to rice.

When the compound of the present invention is used as an active ingredient of a herbicide, it is usually mixed with a solid carrier, a liquid carrier, a surfactant and other auxiliaries for preparation to prepare an emulsion, a wettable powder, a suspending agent,
Formulated in granules, wettable powders and the like. These preparations contain the compound of the present invention as an active ingredient in an amount of 0.005 to 80% by weight,
Preferably, it is contained in an amount of 0.01 to 70%.

Examples of solid carriers include kaolin clay, ttattalgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, walnut flour,
Examples of the liquid carrier include aromatic powders such as xylene and methylnaphthalene, alcohols such as isopropanol, ethylene glycol and cellosolve, acetone, and cyclohexanone. And ketones such as isophorone, vegetable oils such as soybean oil and cottonseed oil, dimethyl sulfoxide, N, N-dimethylformamide, acetonitrile, water and the like.

Surfactants used for emulsification, dispersion, wet spreading, etc. include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkyl aryl ether phosphates. Nonionic surfactants such as anionic surfactants such as ester salts, polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters Is raised. Other auxiliaries for formulation include lignin sulfonate,
Alginate, polyvinyl alcohol, gum arabic,
CMC (carboxymethylcellulose), PAP (acidic isopropyl phosphate) and the like.

The compound of the present invention is usually formulated and subjected to soil treatment, foliage treatment or flooding treatment before or after emergence of weeds. The soil treatment includes a soil surface treatment and a soil admixture treatment. The foliage treatment includes a treatment from above a plant body and a local treatment for treating only weeds so as not to adhere to crops. In addition, it is expected that the herbicidal effect can be enhanced by mixing and using other herbicides. Further, it can be used in combination with insecticides, acaricides, nematicides, fungicides, plant growth regulators, fertilizers, soil conditioners and the like. The compound of the present invention can be used as an active ingredient in paddy fields, fields, orchards, pastures, lawns, forests or non-agricultural lands.

When the compound of the present invention is used as an active ingredient of a herbicide, the amount of treatment varies depending on weather conditions, preparation form, treatment time, method, place, target crop, target weed and the like, but is usually 0.001 per are. 5 g to 80 g, preferably 0.02 g to 40 g, and the emulsions, wettable powders, suspending agents and the like usually have a predetermined amount of 1 liter to 10 liters per are (if necessary, a spreading agent and the like are added. ) Processed by diluting with water, granules and the like are usually processed without dilution. Examples of the spreading agent include polyoxyethylene resin acid (ester), ligninsulfonic acid, abietic acid, dinaphthylmethanedisulfonic acid, paraffin and the like, in addition to the above-mentioned surfactant.

[0045]

Industrial Applicability The compound of the present invention has excellent herbicidal activity against various weeds which are problematic in soil treatment and foliage treatment in upland fields, and in flooding treatment in paddy fields. Since it shows excellent selectivity among weeds, it can be used for various uses as an active ingredient of a herbicide.

[0046]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Production Examples, Formulation Examples and Test Examples, but the present invention is not limited to these Examples. First, Production Examples of the compound of the present invention will be shown.

Production Example 1 (Production of Compound (3) of the Present Invention) Ethyl 3-amino-4,4,4-trifluorocrotonate (2.1 g) and sodium hydride (0.5 g) were added to N,
Dissolved in N-dimethylformamide (0.5 g) and cooled. 7-chloro-5-fluoro-4-methoxycarbonylamino-2-methylbenzo [b] furan 2.
A solution of 0 g in N, N-dimethylformamide (5 g) was added dropwise under ice-cooling, and the mixture was stirred for 30 minutes and heated under reflux for 3 hours. After cooling, methyl iodide (0.6 g) was added, and the mixture was allowed to stand at room temperature overnight. After completion of the reaction, the reaction solution was poured into water, extracted with ethyl acetate, the organic layer was washed with water, dried and concentrated. The obtained residue was purified by silica gel chromatography (developing solvent; hexane: ethyl acetate = 4: 1) to obtain 1.1 g of the desired compound.

Production Example 2 (Production of Compound (3) of the Present Invention) 2.3 g of 7-chloro-5-fluoro-4-methoxycarbonylamino-2-methylbenzo [b] furan was added to N, N-
A solution dissolved in 10 ml of dimethylformamide was added to 1.5 ml of ethyl 3-amino-4,4,4-trifluorocrotonate.
g and 0.2 g of sodium hydride in 10 ml of N, N-dimethylformamide were added dropwise at room temperature. 1
After stirring at 20 ° C. for 3 hours, the mixture was cooled to room temperature, 2.6 g of methyl iodide was added, and the mixture was stirred at room temperature for 2 hours. The reaction solution was poured into water, extracted with ethyl acetate, the organic layer was washed with water, dried,
Concentrated. The obtained residue was purified by silica gel chromatography (developing solvent; hexane: ethyl acetate = 4: 1) to obtain 2.9 g of the desired compound. (Yield: 86%) ¹ H-NMR δ (ppm) (60 MHz, CDC
l ₃ ): 2.33 (3H, s), 3.42 (3H, s), 6.09
(1H, s), 6.20 (1H, s), 6.99 (1H, d, J =
10Hz)

Production Example 3 (Production of Compound (2) of the Present Invention) According to the method of Production Example 2, 0.5 g of 5,7-difluoro-4-methoxycarbonylamino-2-methylbenzo [b] furan was added to 3-amino -4,4,4-Trifluorocrotonate and 0.35 g of methyl iodide,
g, 0.53 g of the target compound was obtained.
(Yield: 71%) ¹ H-NMR δ (ppm) (60 MHz, CDC
l ₃ ): 2.38 (3H, s), 3.48 (3H, s), 6.14
(1H, m), 6.24 (1H, s), 7.78 (1H, t, J
= 10Hz)

Production Example 4 (Production of Compound (5) of the Present Invention) 5,7-difluoro-4-methoxycarbonylamino-
A solution of 0.3 g of 2-methylbenzo [b] furan dissolved in 2 ml of N, N-dimethylformamide was treated with 3-amino-
To a solution of 0.21 g of ethyl 4,4,4-trifluorocrotonate and 0.03 g of sodium hydride in 2 ml of N, N-dimethylformamide was added dropwise at room temperature. Reaction solution 1
After stirring at 20 ° C. for 3 hours, the mixture was cooled to room temperature,
A solution prepared by dissolving 0.3 g of dinitrophenoxyamine in 1 ml of N, N-dimethylformamide was added, and the mixture was stirred at room temperature for 3 hours. The reaction solution was poured into water, extracted with ethyl acetate, and the organic layer was washed with water, dried and concentrated. The obtained residue was purified by silica gel chromatography (developing solvent; hexane: ethyl acetate = 1: 1) to obtain 0.06 g of the desired compound.
(Yield: 13%) ¹ H-NMR δ (ppm) (60 MHz, DMSO-
d6): 2.31 (3H, s), 5.34 (2H, s), 6.19
(1H, s), 6.55 (1H, m), 7.20 (1H, t, J
= 10Hz)

Production Example 5 (Production of Compound (8) of the Present Invention) 4-Amino-7-chloro-5-fluoro-2-methylbe
2.6 g of benzo [b] thiophene were dissolved in 10 ml of toluene.
11.9 g of phosgene was dissolved in 20 ml of toluene.
The solution was added dropwise at room temperature. The reaction was heated at reflux for 2 hours
After that, the excess phosgene is distilled off and the isocyanate derivative
20 ml of a toluene solution of was obtained. This solution is
1.6 g of ethyl -4,4,4-trifluorocrotonate
And 0.29 g of sodium hydride in N, N-dimethylform
The solution dissolved in 10 ml of amide was added dropwise at 5 ° C. Next
3.4 g of methyl iodide was added dropwise at 5 ° C.
Stirred at room temperature for 2 hours. Pour the reaction solution into water and add ethyl acetate
After extraction, the organic layer was washed with water, dried and concentrated. Got
The residue is subjected to silica gel chromatography (developing solvent;
Purification with sun: acetic acid = 3: 1) gave 1.7 g of the desired compound.
Was. (Yield: 36%) ¹ H-NMR δ (ppm) (60 MHz, CDC
l_Three): 2.54 (3H, s), 3.54 (3H, s), 6.33
(1H, s), 6.67 (1H, s), 7.15 (1H, d, J
= 9Hz)

Production Example 6 (Production of Compound (14) of the Present Invention) 1- (7-Chloro-2-ethyl-5-fluorobenzo [b] furan-4-yl) -4-trifluoromethyl-
1.9 g of 1,2,3,6-tetrahydropyrimidine-2,6-dione and 0.3 g of sodium hydride were dissolved in 10 ml of N, N-dimethylformamide, and after cooling to room temperature, 0.8 g of methyl iodide was added dropwise. And stirred for 30 minutes.
After completion of the reaction, the reaction solution was poured into water and extracted with ethyl acetate.
The organic layer was washed with water, dried and concentrated. The obtained residue was purified by silica gel chromatography (developing solvent; hexane: ethyl acetate = 4: 1) to obtain 0.7 g of the desired compound. (Yield: 36%) ¹ H-NMR δ (ppm) (500 MHz, CDCl
₃ ): 1.33 (3H, t, J = 8 Hz), 2.75 (2H, d
q, J = 8 Hz (d), 1 Hz (q)), 3.58 (3H,
s), 6.24 (1H, t, J = 1 Hz), 6.39 (1H,
s), 7.15 (1H, d, J = 10Hz)

Production Example 7 (Production of Compound (14) of the Present Invention) 1- [4-Chloro-2-fluoro-5- (1-methyl-
2-propynyloxy) phenyl] -3-methyl-4-
To a solution of 1.1 g of trifluoromethyl-1,2,3,6-tetrahydropyrimidine-2,6-dione in 2 ml of mesitylene was added 0.16 g of potassium fluoride at room temperature, and the mixture was heated under reflux for 2 hours. After cooling to room temperature, potassium fluoride was filtered off, the solvent was distilled off, and the residue was purified by silica gel chromatography (developing solvent; hexane: ethyl acetate = 4: 1) to obtain 0.38 g of the desired compound. (Yield: 35%)

Production Example 8 (Production of Compound (17) of the Present Invention) 0.01 g of 60% sodium hydride was suspended in 20 ml of dimethylformamide, and 3-amino-1- [4-chloro-2-fluoro-5 was added thereto. -(1-methyl-2-propynyloxy) phenyl] -4-trifluoromethyl-1,
2,3,6-tetrahydropyrimidine-2,6-dione
0.71 g was added at room temperature, and the mixture was stirred at 100 ° C. for 2 days. After completion of the reaction, the reaction solution was allowed to cool to room temperature, poured into ice water, and extracted with ethyl acetate. The extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography (developing solvent; hexane: ethyl acetate = 3: 1) to obtain 0.15 g of the desired compound. (Yield: 21%) ¹ H-NMR δ (ppm) (60 MHz, CDC
_{l 3): 1.30 (3H,} t, J = 8Hz), 2.79 (2H,
dq, J = 8 Hz (d), 1 Hz (q)), 4.58 (2
H, s), 6.18 (1H, t, J = 1 Hz), 6.21 (1
H, s), 7.07 (1H, d, J = 10 Hz)

Table 1 shows the compounds of the present invention produced according to the above Production Examples.

[0056]

[Table 1]

Next, production examples of the starting compound of the compound of the present invention will be shown.

Production Example 9 (Production of Compound [II]) 2-chloro-4-fluoro-5-nitrophenol 20.3
g and 11.7 g of 2,3-dichloropropene were dissolved in 200 ml of N, N-dimethylformamide, and 14.6 g of potassium carbonate was added thereto at room temperature, followed by stirring at 80 ° C. for 2 hours. After completion of the reaction, the reaction solution was cooled to room temperature, poured into water, extracted with ethyl acetate, and the organic layer was washed with water, dried and concentrated. The obtained residue is purified by silica gel chromatography (developing solvent; hexane: ethyl acetate = 4: 1) to obtain 14.8 g of 4-chloro-5- (2-chloro-2-propenyloxy) -2-fluoronitrobenzene. Was.
(Yield 53%) ¹ H-NMR δ (ppm) (60 MHz, CDC
l ₃ ): 4.55 (2H, s), 5.38 (1H, br), 5.51
(1H, br), 7.21 (1H, d, J = 10 Hz), 7.
45 (1H, d, J = 6Hz)

12.8 g of 4-chloro-5- (2-chloro-2-propenyloxy) -2-fluoronitrobenzene obtained above was dissolved in 50 ml of ethyl acetate. next,
13.4 g of iron powder was suspended in a mixture of 200 ml of acetic acid and 20 ml of water, and the above ethyl acetate solution was added to 80 ml with vigorous stirring.
The mixture was added dropwise at 10 ° C over 10 minutes and stirred at 80 ° C for 0.5 hour.
After completion of the reaction, the reaction solution was cooled to 60 ° C., and ethyl acetate 5
00 ml was added, and the insolubles were filtered off. The filtrate was washed with 5% NaHCO
_{3 After} washing with an aqueous solution and removing acetic acid, drying and concentration,
11.5 g of 4-chloro-5- (2-chloro-2-propenyloxy) -2-fluoroaniline was obtained. ¹ H-NMR δ (ppm) (60 MHz, CDC
l ₃ ): 3.6-3.9 (2H, br), 4.51 (2H, s),
5.41 (1H, br), 5.60 (1H, br), 6.33 (1
H, d, J = 8 Hz), 6.98 (1 H, d, J = 10 H)
z)

4-Chloro-5- (2-chloro-2-propenyloxy) -2-fluoroaniline obtained above
Dissolve 10.4 g in N, N-diethylaniline 20 ml,
The mixture was heated under reflux for 12 hours. After the completion of the reaction, the reaction solution was cooled to room temperature and dissolved in ethyl acetate. After washing three times with 10% hydrochloric acid to remove N, N-diethylaniline, drying,
Concentrated. The obtained residue was purified by silica gel chromatography (eluent: hexane: ethyl acetate = 4: 1) to give 3-amino-6-chloro-2- (2-chloro-2-).
7.4 g of (propenyl) -4-fluorophenol were obtained.
(Yield 71%) mp 50.5-51.5 ° C. ¹ H-NMR δ (ppm) (60 MHz, CDC
l ₃ ): 3.67 (2H, s), 3.6-3.9 (2H, br),
5.05 (1H, br), 5.20 (1H, br), 5.43 (1
H, s), 6.89 (1H, d, J = 10 Hz)

Production Example 10 (Production of Compound [III]) 3-amino-6-chloro-2- (2-chloro-2-propenyl) -4-fluorophenol 4.8 obtained above.
g was dissolved in 20 ml of chloroform, and 4.6 g of trifluoromethanesulfonic acid was added dropwise to this solution at 5 ° C over 5 minutes, and then stirred at room temperature for 5 hours. After completion of the reaction, the reaction solution was poured into 30 ml of a 5% aqueous solution of NaOH at 5 ° C, extracted with ethyl acetate, dried and concentrated to give 4-amino-7-chloro-5-.
3.5 g of fluoro-2-methylbenzo [b] furan were obtained. (Yield: 86%)

Production Example 11 (Production of compound [III]) 5-Amino-2-chloro-4-fluorothiophenol
8.89 g and 3.5 g of anhydrous potassium carbonate are added to 100 ml of N, N-dimethylformamide, and then the mixture is added to 2,3-
6.65 g of dichloropropene was added and the mixture was stirred at 20-40 ° C for 4 hours. After completion of the reaction, the reaction solution was extracted with ether, washed with water, dried and concentrated. The obtained residue is subjected to silica gel chromatography (developing solvent; hexane: ethyl acetate = 7:
Purified in 1), 4-chloro-2-fluoro-5- (2-
10.5 g of chloro-2-propenylthio) aniline were obtained.
(Yield: 84%)

The 4-chloro-2-fluoro-5- (2-chloro-2-propenylthio) aniline 1 obtained above
0.0 g was dissolved in 25 ml of N, N-diethylaniline,
Heated to reflux for an hour. Next, the reaction solution was allowed to cool to room temperature, and
The pH was adjusted to 2 by adding 0% hydrochloric acid, and the mixture was stirred at room temperature for 1 hour. The reaction solution was extracted with ethyl acetate, washed with water, dried and concentrated. The obtained residue was crystallized and washed with a hexane-ether mixture to give 3.4 g of 4-amino-7-chloro-5-fluoro-2-methylbenzo [b] thiophene.

Some of the compounds [III] obtained according to Production Examples 10 and 11 are shown in Table 2.

[0065]

[Table 2]

Production Example 12 (Production of Compound [IV]) 3.4 g of 4-amino-7-chloro-5-fluoro-2-methylbenzo [b] furan and 2.6 g of N, N-diethylaniline were dissolved in 20 ml of tetrahydrofuran. Then, 1.6 g of methyl chlorocarbonate was added dropwise thereto at room temperature, and the mixture was heated under reflux for 3 hours. After completion of the reaction, the reaction solution was cooled to room temperature, dissolved in ethyl acetate, washed with 10% hydrochloric acid to remove N, N-diethylaniline, dried and concentrated. The obtained residue was washed with hexane to obtain 3.8 g of 7-chloro-5-fluoro-4-methoxycarbonylamino-2-methylbenzo [b] furan. (Yield: 87%) mp, 168-169 ° C ¹ H-NMR δ (ppm) (60 MHz, CDC
l ₃ ): 2.30 (3H, s), 3.71 (3H, s), 6.20
(1H, br), 6.30 (1H, s), 7.09 (1H, d,
J = 10Hz)

Production Example 13 (Production of Compound [IV]) According to Production Example 12, 4-amino-5,7-difluoro-2-methylbenzo [b] furan was reacted with methyl chlorocarbonate to give 5, 7-Difluoro-4-methoxycarbonylamino-2-methylbenzo [b] furan was obtained. mp, 156-158 ° C ¹ H-NMR δ (ppm) (60 MHz, DMSO-
d6): 2.26 (3H, s), 3.45 (3H, s), 6.39
(1H, br), 7.00 (1H, t, J = 11 Hz), 9.
05 (1H, br)

Next, preparation examples will be shown. The compounds of the present invention are shown by the compound numbers in Table 1. Parts are parts by weight. Formulation Example 1 Compounds of the present invention (1) to (5), (8), (14), (1
7), (25) and (49) 50 parts each, 3 parts of calcium ligninsulfonate, 2 parts of sodium lauryl sulfate and 45 parts of synthetic hydrous silicon oxide are thoroughly pulverized and mixed to obtain wettable powders. Formulation Example 2 Compounds of the present invention (1) to (5), (8), (14), (1
7), (25) and (49), 5 parts each, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate, 25 parts of xylene and 50 parts of cyclohexanone are mixed well to obtain emulsions.

Formulation Example 3 Compounds of the present invention (1) to (5), (8), (14), (1)
7), (25), (49) 2 parts each, synthetic hydrous silicon oxide 1
Parts, 2 parts of calcium ligninsulfonate, 30 parts of bentonite and 65 parts of kaolin clay are well pulverized and mixed,
After adding water and kneading well, the mixture is granulated and dried to obtain granules. Formulation Example 4 Compounds of the present invention (1) to (5), (8), (14), (1
7), (25), (49) each 25 parts, polyoxyethylene sorbitan monooleate 3 parts, CMC 3 parts and water 6
9 parts are mixed well and wet-pulverized until the particle size becomes 5 microns or less to obtain a suspending agent. Formulation Example 5 Compounds of the present invention (1) to (5), (8), (14), (1)
7), (25), (49) 0.05 parts each, synthetic hydrous silicon oxide 1
Parts, 2 parts of calcium ligninsulfonate, 30 parts of bentonite, and 66.95 parts of kaolin clay, are well pulverized and mixed, water is added and kneaded well, and the mixture is granulated and dried to obtain granules.

Next, Test Examples show that the compounds of the present invention are useful as active ingredients of herbicides. The compounds of the present invention are indicated by the compound numbers in Table 1, and the compounds used for comparison are indicated by the compound symbols in Table 3.

[0071]

[Table 3]

In the evaluation of the herbicidal efficacy and the phytotoxicity, the test plants (weeds and crops) at the time of the survey were evaluated as “0” when there was no or almost no difference in the state of emergence and growth from the untreated plants. , The test plant is completely withered or the germination or growth is completely suppressed as "5", and classified into 6 stages of 0 to 5, 0, 1, 2, 3, 4,
Indicated by 5.

Test Example 1 Upland Soil Surface Treatment Test Upland soil was packed in a cylindrical plastic pot having a diameter of 10 cm and a depth of 10 cm, and seeds of barnyard grass, Malva morning glory, and strawberry were sowed and covered with soil. A test compound was prepared into an emulsion according to Formulation Example 2, and a predetermined amount thereof was diluted with 10 liters of water per are and treated on the soil surface with a small sprayer. After processing 2
They were grown in a greenhouse for 0 days and their herbicidal efficacy was investigated. Table 4 shows the results.

[0074]

[Table 4]

Test Example 2 Upland foliage treatment test Upland soil was packed in a cylindrical plastic pot having a diameter of 10 cm and a depth of 10 cm, and barley, malva morning glory, radish and strawberry were sowed, covered with soil and grown in a greenhouse for 10 days. Thereafter, the test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount thereof was diluted with water containing a spreading agent equivalent to 10 liters per are, and foliage treatment was performed from above the plant with a small sprayer. After the treatment, the plants were raised in a greenhouse for 20 days, and the herbicidal efficacy was examined. Table 5 shows the results.

[0076]

[Table 5]

Test Example 3 Paddy Field Flooding Treatment Test Paddy soil was packed in a cylindrical plastic pot having a diameter of 8 cm and a depth of 12 cm, and seeds of radish and broadleaf weeds (Azena, Kikasigusa, Mizohakobe) were sown at a depth of 1 to 2 cm. did.
After being submerged to a paddy field, rice at the two leaf stage was transplanted and grown in a greenhouse. Six days later (early stage of the emergence of each weed), the test compound was made into an emulsion according to Preparation Example 2, and a predetermined amount of the emulsion was diluted with 5 ml of water and applied to the water surface. After the treatment, they were raised in a greenhouse for 20 days, and their herbicidal efficacy and phytotoxicity were investigated. Table 6 shows the results.

[0078]

[Table 6]

Test Example 4 Field Soil Treatment Test A bat having an area of 33 × 23 cm ² and a depth of 11 cm was filled with field soil, and cotton, corn, malva asagao, ichibi,
Dogwood physalis, dog millet, and Achinoekorogosa were sown and covered to a depth of 1 to 2 cm. A test compound was prepared into an emulsion according to Formulation Example 2, and a predetermined amount thereof was diluted with 10 liters of water per are and treated on the soil surface with a small sprayer. After the treatment, they were raised in a greenhouse for 20 days, and their herbicidal efficacy and phytotoxicity were investigated. Table 7 shows the results.

[0080]

[Table 7]

Test Example 5 Upland Soil Treatment Test A vat having an area of 33 × 23 cm ² and a depth of 11 cm was filled with upland soil, and soybeans, rice, ibis and dogwood were sowed.
The soil was covered to a depth of 1-2 cm. A test compound was prepared into an emulsion according to Formulation Example 2, and a predetermined amount thereof was diluted with 10 liters of water per are and treated on the soil surface with a small sprayer. After the treatment, they were raised in a greenhouse for 20 days, and their herbicidal efficacy and phytotoxicity were investigated. Table 8 shows the results.

[0082]

[Table 8]

Test Example 6 Upland Soil Treatment Test A bat having an area of 33 × 23 cm ² and a depth of 11 cm was filled with upland soil, and cotton, American stag, spurges, ibis, and Achinoekorogosa were sown and covered to a depth of 1-2 cm. did. A test compound was prepared into an emulsion according to Formulation Example 2, and a predetermined amount thereof was diluted with 10 liters of water per are and treated on the soil surface with a small sprayer. After the treatment, they were raised in a greenhouse for 20 days, and their herbicidal efficacy and phytotoxicity were investigated. Table 9 shows the results.

[0084]

[Table 9]

Test Example 7 Field Soil Surface Treatment Test A bat having an area of 33 × 23 cm ² and a depth of 11 cm was stuffed with field soil, and wheat, Sanaedade, Hakobe, Oinunowoguri, field pansies, and Suzumeokatabira were sown.
The soil was covered to a depth of 1-2 cm. A test compound was prepared into an emulsion according to Formulation Example 2, and a predetermined amount thereof was diluted with 10 liters of water per are and treated on the soil surface with a small sprayer. After the treatment, they were raised in a greenhouse for 27 days, and their herbicidal efficacy and phytotoxicity were investigated. Table 10 shows the results.

[0086]

[Table 10]

[0087] Test Example 8 upland foliage treatment test area 33 × 23cm ^2, filled with upland soil vat depth 11cm, seeded Ipomoea purpurea, cocklebur, velvetleaf, black nightshade, and barnyardgrass were grown for 18 days. Thereafter, the test compound was emulsified in accordance with Formulation Example 2, and a predetermined amount thereof was diluted with 10 liters of water per areal containing a spreading agent, and uniformly spread over the entire foliage from above the plant using a small sprayer. Processed. At this time, the growth status of the weeds varies depending on the species, but the height of the plant was 6 to 30 cm at the 1 to 4 leaf stage. Processing 20
One day later the herbicidal efficacy was investigated. Table 11 shows the results.
This test was performed in a greenhouse throughout the entire period.

[0088]

[Table 11]

Test Example 9 Upland Field Foliage Treatment Test A bat having an area of 33 × 23 cm ² and a depth of 11 cm was filled with upland soil, and Sanaetade, Yaemgra, Oinunowuguri and field pansies were sown, covered with a soil of 1-2 cm in depth, and covered with soil.
They were raised in a greenhouse for one day. A test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount thereof was diluted with water containing a spreading agent equivalent to 10 liters per are, and the whole surface of the foliage was uniformly treated from above the plant with a small sprayer. . At this time, the growth status of weeds and crops differed depending on the grass species, but the plant height was 2 to 12 cm at the 1 to 4 leaf stage. The herbicidal efficacy was examined 27 days after the treatment. Table 12 shows the results. This test was performed in a greenhouse throughout the entire period.

[0090]

[Table 12]

────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Shoji Sakaki 4-2-1 Takashi, Takarazuka-shi, Hyogo Sumitomo Chemical Industries Co., Ltd. (72) Inventor Ryo Sato 4-2-1 Takashi Takarazuka-shi, Hyogo Sumitomo Within Chemical Industry Co., Ltd. (72) Inventor Eiki Nagano 4-2-1 Takashi, Takarazuka-shi, Hyogo Prefecture Within Sumitomo Chemical Co., Ltd. (58) Field surveyed (Int. Cl. ⁶ , DB name) C07D 405/04 C07D 307/79 C07D 333/54 C07D 409/04 CA (STN) REGISTRY (STN)

Claims (5)

(57) [Claims] 1. A compound represented by the general formula: [Wherein, R represents a lower alkyl group, A represents a hydrogen atom,
X represents an oxygen atom or a sulfur atom; X represents a hydrogen atom, a fluorine atom, a chlorine atom or a bromine atom; and Z represents a methyl group or an amino group. A benzofuran derivative represented by the formula: 2. A compound represented by the general formula: [Wherein, R represents a lower alkyl group, A represents a hydrogen atom,
X represents a fluorine atom or a chlorine atom, X represents an oxygen atom or a sulfur atom, and Y represents a hydrogen atom, a fluorine atom, a chlorine atom or a bromine atom. A compound represented by the formula:
Formula Formula 3 embedded image CH ₃ -E [wherein, E represents a chlorine atom, a bromine atom, an iodine atom or a methanesulfonyloxy group. Or NH ₂ -G wherein G represents a methanesulfonyloxy group, a p-toluenesulfonyloxy group or a 2,4-dinitrophenoxy group. The method for producing a benzofuran derivative according to claim 1, wherein the compound is reacted with a compound represented by the following formula: 3. A compound represented by the general formula: Wherein R ′ and R ″ are the same or different from each other;
A represents a hydrogen atom or a lower alkyl group, A represents a hydrogen atom, a fluorine atom or a chlorine atom, X represents an oxygen atom or a sulfur atom, Y represents a hydrogen atom, a fluorine atom,
Z represents a chlorine atom or a bromine atom, and Z represents a methyl group or an amino group. 2. The method for producing a benzofuran derivative according to claim 1, wherein the compound is reacted in the presence of a base. 4. A herbicide comprising the benzofuran derivative according to claim 1 as an active ingredient. 5. A compound represented by the general formula: Wherein R ′ and R ″ are the same or different from each other;
A represents a hydrogen atom or a lower alkyl group, A represents a hydrogen atom, a fluorine atom or a chlorine atom, X represents an oxygen atom or a sulfur atom, Y represents a hydrogen atom, a fluorine atom,
Represents a chlorine atom or a bromine atom. ] The compound shown by these.