JP3117371B2 - Furobenzopyran derivatives and herbicides containing them as active ingredients - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel furobenzopyran derivative, a process for producing the same, and a herbicide containing the same as an active ingredient.

[0002]

2. Description of the Related Art There are very few synthetic examples of compounds having a furobenzopyran ring, and no compounds exhibiting herbicidal activity are known at all. Only monoserine (MONOCERIN) represented by the following structural formula (Chemical Formula 3) has been reported to exhibit physiological activity as a furobenzopyran derivative.

[0003]

Embedded image This compound is described as an antibacterial metabolite of Helminthosporium monoceras by J.I. Chem. Soc. (C) 2598
(1970). Further, it is described in US Pat. No. 3,661,935 as an antibacterial compound.

[0004] In addition, O. R. Martin et al. Carb
ohydr. Res. , 196 , 41-58 (199).
0) describes a compound group represented by the following formula (Formula 4).

[0005]

Embedded image In addition, O. R. Martin is in Carbohydr. R
es. , 171 , 211-222 (1987) describe the following compounds (Chemical Formulas 5 and 6).

[0006]

Embedded image

[0007]

Embedded image However, even for these compounds, there is no description as to the presence or absence of physiological activity including herbicidal activity.

[0008]

Many herbicides for fields or paddy fields have been developed to date, but there is no sufficient herbicidal activity or selectivity for crops.

Accordingly, an object of the present invention is to find a compound which does not cause harm to useful crops under any conditions and which has excellent herbicidal activity when used in fields and paddy fields.

[0010] That is, while the present invention is sufficiently safe against paddy rice, it shows strong herbicidal activity against annual weeds such as Nobie, Tamaya-tsuri, Konagi, Kika-shigusa and perennial weeds such as Firefly, Spodoptera striata, Krogwai, and Matsubai. Another object of the present invention is to provide a compound having excellent performance as a rice herbicide.

In a field, soil treatment or foliage treatment can be used to control the crabgrass, chickweed, polyplum, inoubyu, kogokeyatsuri, pureruhiyu, noborogiku, shiroza, hamasuge,
Convolvulus, clover, yamgra, sparrow,
It is an object of the present invention to provide a compound which is effective also for Aspergillus oryzae, Japanese radish, Enochorogosa, etc., and is effective not only as a herbicide for paddy rice but also as a field-acting herbicide and other herbicides for non-agricultural land.

[0012]

Means for Solving the Problems and Actions The present inventors have synthesized a large number of novel furobenzopyran compounds in order to solve the above-mentioned problems, and have studied variously on their herbicidal activity. As a result, they have found a compound that is not only effective as a paddy rice herbicide, but also as a field-acting herbicide and other herbicides for non-agricultural lands, and completed the present invention.

That is, the present invention relates to a compound represented by the general formula (I):

[0014]

Embedded image[Where R₁ Represents a lower alkyl group;_Two Is lower alk
Group, lower alkoxy group, halogen atom or halogen
Represents a substituted lower alkyl group;_Three Is lower alkyl group, lower
Lower alkoxy group, halogen atom, halogen-substituted lower alkyl
Represents a kill group, a phenoxy group or a benzyloxy group,
R_Four Represents a hydrogen atom or a lower alkyl group;_Five Ha
Ano group, nitro group, phenyl group, group -S (O)_qR₆ ,
Group-0S0_TwoR₆ , Group -XC (= O) R₆, Group -XR₇,
The group -XCH (R₉) C (= O) R₈, Group -XP (= X)
(XR₆)_Two, Group -N (R₉) R_Ten, Group -N (R₉) C (=
X) R₁₁, Group -N (R₉) SO_TwoR₆ , Group -C (R₉)_TwoO
R_Ten, Group -CH (R₉) S (O)_qR₆, Group -CH (R₉)
XC (= 0) R₁₁, Group -CH (R₉) N (R₉) R_Ten, Basis
-CH (R₉) N (R₉) C (= X) R₁₁, Group -CH (R
₉) XP (= X) (XR₆) _Two, Group -C (= X) R₈ , Basis
-CH (XR₁₂) XR₁₃, A group -C (= X) N (R₁₄) R
₁₅, Group -CH = NR₈ , Group -CH = CR₁₆R₁₇, Group -O
｛C (R₁₈)_Two｝_r-O- (adjacent carbons on the benzene ring
Linking the atoms to form a 5- or 6-membered ring) or a group-
｛C (R₁₈)_Two｝_s-(Adjacent carbon atoms on the benzene ring
To form a 5- or 6-membered ring);
₆ Is a lower alkyl group or (lower alkyl group, lower alkyl
Phenyl, which may be substituted with a oxy group or a halogen atom)
R represents a group₇ Is a hydrogen atom, halogen-substituted lower alkyl
Or an alkoxyalkyl group,₈ Is hydrogen field
, Hydroxy group, lower alkyl group, lower alkoxy
A lower alkylthio group or a phenoxy group;
₉ Represents a hydrogen atom or a lower alkyl group;_TenIs hydrogen
Atom, lower alkyl group, halogen-substituted lower alkyl group
Or an aralkyl group;₁₁Is a lower alkyl group, halo
Gen-substituted lower alkyl group, (lower alkyl group, lower alkyl group
Phenyl, which may be substituted with a oxy group or a halogen atom)
Group, lower alkoxy group, phenoxy group, lower alkyl group
Represents a mino group or an anilino group;₁₂, R₁₃Are each
Hydrogen atom or lower alkyl group or R₁₂And R₁₃Together
And cyclized to-(CH_Two)_Two-Or-(CH_Two)_Three-
Represents, R₁₄Represents a hydrogen atom or a lower alkyl group;
₁₅Represents a hydrogen atom, a lower alkyl group, a (lower alkyl group,
A alkoxy group or a halogen atom)
Phenyl or R₁₄And R₁₅Together with oxygen atoms, sulfur
5 or 6 members which may contain yellow or nitrogen atoms
Represents a ring, R₁₆Is hydrogen atom, cyano group or lower alcohol
X represents a carbonyl group; ₁₇Is hydrogen atom, lower alkyl
Group, nitro group, cyano group or lower alkoxycarbo
Represents a phenyl group;₁₈Is a hydrogen atom, a lower alkyl group or
X represents a halogen atom, and X represents an oxygen atom or a sulfur atom.
Q is an integer of 0 to 2, r is 1 or 2, and s is 3
Or 4 ｝ M is an integer of 0-4, n is an integer of 0-2
And p represents an integer of 1 to 3, and m, n and p are 2 or more.
When above, R_Two , R_Three And R_Five Are the same but different
May be. Furbenzobenzopyran derivatives represented by the formula:
And characterized by containing them as active ingredients
It is a herbicide.

In the compound of the present invention, a lower alkyl group,
A lower alkoxy group or a lower acyl group refers to an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or an acyl group having 1 to 4 carbon atoms, and a halogen atom is a fluorine atom, a chlorine atom, or a bromine. Atom, iodine atom.

The compound (I) of the present invention is a novel compound,
These are represented by the following reaction formula 1

[0017]

Embedded image (Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , m, n and p represent the above-mentioned meanings, R ₁₉ represents a lower alkyl group or a lower acyl group, Z represents a halogen atom, an ester residue And a reactive residue such as the above.) Can be produced by subjecting a tetrahydrofuran derivative represented by the general formula (II) to an intramolecular cyclization reaction. Alternatively, the obtained furobenzopyran derivative can be introduced into another compound of the general formula (I) by introducing or converting a commonly used substituent. As an example, the introduction or conversion example of the substituent R ₅ is shown in the following reaction formula 2 (Chemical formula 9),
0).

[0018]

Embedded image

[0019]

Embedded image [Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₈ , R ₉ , R ₁₁ , R
₁₄ , R ₁₅ , m, and n represent the same meaning as described above. Hereinafter, the production method of the compound (I) of the present invention will be described in detail.

The compound represented by the general formula (III) is a known compound. Org. Chem. , 50 , 478
6 (1985), and US Pat. No. 4,534,534.
785 can be easily synthesized. Usually, they are obtained as a mixture of α- and β-forms, but it is also possible to separate the isomers by silica gel chromatography or the like and use them in the next reaction.

In the reaction scheme 1, the compound of the general formula (II) is converted into a compound of the general formula (III) by n-hexane, benzene, toluene, xylene and diethyl ether in Step A.
In an inert solvent such as ter, dioxane, tetrahydrofuran, dimethylformamide, dimethylsulfoxide, chlorobenzene, methylene chloride, chloroform, methyl ethyl ketone, acetone, acetonitrile, potassium carbonate, sodium carbonate, sodium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydride, It is obtained by using an inorganic base such as sodium amide and reacting with an equivalent amount or a slight excess of the substituted benzyl derivative of the general formula (IV). Alternatively, the reaction can be performed in a two-layer system of an organic solvent such as benzene or toluene and water in the presence of a phase transfer catalyst such as a quaternary ammonium salt or a phosphate. Reaction temperature is -30 ° C
To the boiling point of the solvent, but preferably from room temperature to 60
It is advantageous to carry out the reaction in the range of ° C. After completion of the reaction, post-treatment is carried out as usual, and the target compound can be purified by recrystallization or column chromatography.
The compound of the general formula (II) wherein R ₁₉ is an acyl group can be prepared from a compound of the general formula (II) wherein R ₁₉ is an alkyl group by a known general method (for example, Chem. I).
nd. , 27 , 547 (1968)).

When R ₄ is a hydrogen atom, the resulting compound of the general formula (II) is a mixture of two isomers of α and β anomers in substantially the same ratio as the starting compound of the general formula (III). These can be separated into isomers by silica gel chromatography or the like, and can be used for the next reaction after separation. When R ₄ is a lower alkyl group, there are four types of diastereomers as shown in the following chemical structural formula (Formula 11). Of these, the α and β anomers can be separated by silica gel chromatography or the like, and can be used for the next reaction after separation.

[0023]

Embedded image The compound of the general formula (I) of the present invention is obtained by converting the compound of the general formula (II) into n-hexane, nitrobenzene, chlorobenzene, methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, carbon disulfide, In an inert solvent such as acetonitrile, tin tetrachloride, titanium tetrachloride, aluminum chloride, ferric chloride, Lewis acid such as boron trifluoride diethyl ether complex or sulfuric acid, nitric acid, hydrochloric acid,
It is obtained by an intramolecular cyclization reaction in the presence of a mineral or organic acid such as chlorosulfonic acid, phosphoric acid, benzenesulfonic acid, trifluoromethanesulfonic acid and the like. The reaction temperature can be from -70 ° C to the boiling point of the solvent, but it is more advantageous to carry out the reaction in a relatively low temperature range, and the preferred temperature is from -70 to 30 ° C. After completion of the reaction, post-treatment is carried out as usual, and the target compound can be obtained by recrystallization or purification by column chromatography. The compound of the general formula (I) obtained here is a single optically active compound when R ₄ is a hydrogen atom, but has two diastereomers represented by the following chemical structural formula (Chemical formula 12) when it is a lower alkyl group. Is obtained as

[0024]

Embedded image This diastereomer mixture can be separated by silica gel chromatography or the like, and both compounds have high herbicidal activity as apparent from the test examples. Accordingly, the present invention includes both the diastereomers shown in the above chemical structural formulas.

When the production route of the present invention is arranged in consideration of the absolute configuration of the compounds of the general formulas (II) and (I), the reaction formula 4 when R ₄ is a hydrogen atom is shown below.
3) and reaction formula 5 when R ₄ is a lower alkyl group
(Formula 14)

[0026]

Embedded image

[0027]

Embedded image When R ₄ is a lower alkyl group, two kinds of diastereomers can be usually obtained as described above, but a desired single optically active compound can be obtained by using an optically active compound of the general formula (II). Is also possible. The optically active compound of the general formula (II) is obtained, for example, by reacting the optically active compound of the general formula (IV) in the step (A).

In the embodiment of the present invention, when R ₄ is a lower alkyl group, a mixture of four isomers of the compound of the formula (II) or a compound obtained by separating them into α and β anomers is used in the reaction. The two diastereomers obtained therefrom are separated by silica gel chromatography. At this time, silica gel chromatography (developing solvent; n-hexane:
The diastereomer eluted first with ethyl acetate) was described as Compound A, and the diastereomer eluted later with Compound B. Table 2 shows ¹ H-NMR of the compounds of the present invention. Diastereomers A and B can be classified also based on the assignment of the 5-position proton. For example, when R ₄ is a methyl group, the 5-position proton is observed at about 4.6 ppm in diastereomer A and at about 5.0 ppm in B. As described above, diastereomers A and B both have herbicidal activity.

As another method for synthesizing the compound of the present invention, there is a method of introducing a new substituent or converting a substituent to a furobenzopyran derivative obtained by an intramolecular cyclization reaction. The introduction or conversion of the substituent used here can be carried out by a well-known organic synthesis technique. The above-mentioned reaction formulas 2 and 3, which are one example,
Will be described below.

The reaction formula (2) is an introduction example when the substituent R ₅ is an amino derivative. For example, a compound of the general formula (VI) is obtained by an intramolecular cyclization reaction.
Can be obtained by a conventional nitration reaction using a mixed acid of nitric acid and sulfuric acid in the step (C). Then the substituent R
The compound of the general formula (VII) wherein ₅ is an amino group can be obtained by subjecting the compound of the general formula (VI) to a reduction reaction such as a normal pressure hydrogenation reaction in the step (D). General formula (VII
The compound (I) can be easily obtained by reacting the compound of the general formula (VII) with a lower alkyl halide or an acid chloride in an inert solvent in the presence of an organic or inorganic base in the step (E).

The reaction formula (3) shows an example of introduction of a substituent when the substituent R ₅ is a carboxylic acid derivative. For example, the compound of the general formula (X) is a compound of the general formula (I) wherein one of the substituents R ₃ obtained by the intramolecular cyclization reaction is a chloromethyl group.
It is obtained by reacting the compound of X) with 2-nitropropane in an inert solvent in the presence of a base such as sodium methoxide in step (F). The compound of the general formula (XI) can be obtained by subjecting the compound of the general formula (X) to an oxidation reaction using chromic acid, hydrogen peroxide or the like in step (G). The compound of the general formula (XII) is obtained by subjecting the compound of the general formula (X) to a dehydration reaction with an amine derivative in an inert solvent in step (H). General formula (XII
The compound (I) is obtained by converting the compound of the general formula (XI) into an acid chloride using thionyl chloride or the like in the step (J), or an intermediate obtained by activating a carbonyl group using carbonyldiimidazole or the like; It is obtained by reacting with an amine derivative in the presence of an inorganic or organic base in a solvent. When X is a sulfur atom in the compound of the general formula (XIII), it can be easily obtained by reacting a compound in which X is an oxygen atom using a Lawson reagent or the like.

The compound of the general formula (I) of the present invention is extremely safe for paddy rice, while
It shows strong herbicidal activity against annual weeds such as oaks and stags and perennial weeds such as fireflies, sedges, black croakers and pine trees, and has excellent performance as a herbicide for paddy rice. Also, in any of soil treatment or foliage treatment, soybean, cotton, sugar beet, corn, sugarcane, has a high selectivity to useful crops such as wheat, and Meishishiba, Hakobe, Tade, Inubiyu, Kogomeyatsuri, Suberihigyu, Noborogiku, Shiroza, Hamasue, Convolvulus,
It has herbicidal activity on clover, yamgra, sparrow lily, spruce velvet, locust, enokorogusa, etc., and is effective not only as a herbicide for paddy rice but also as a field-acting herbicide and other herbicides for non-agricultural lands.

The compound (I) of the present invention may be used as it is for the plant to be treated, but it is generally mixed with an inert liquid or solid to prepare a generally used preparation.
For example, it is used after adjusting to powders, granules, wettable powders, emulsions, flowable preparations and the like. If necessary for the preparation, an auxiliary agent can be added.

As the carrier, any solid or liquid carrier can be used as long as it is generally used for agricultural and horticultural medicines, and it is not limited to a specific one. For example, solid carriers include mineral powders such as clay, talc, bentonite, calcium carbonate, diatomaceous earth, white carbon, etc., vegetable powders such as soybean powder, starch, petroleum resins, polyvinyl alcohol, polyalkylene glycols and the like. Molecular compounds, urea, waxes and the like. Examples of the liquid carrier include various oils, various organic solvents, water and the like.

As auxiliary agents, surfactants, binders, stabilizers and the like which are usually used in agricultural and horticultural medicines can be used alone or in combination as necessary. Further, in some cases, an industrial bactericide or a bactericidal / antifungal agent can be added for bactericidal / fungal control.

As the surfactant, nonionic, anionic, cationic and amphoteric surfactants can be used as appropriate. Preferred examples include alkyl phenols, higher alcohols, alkyl naphthols, higher fatty acids, fatty acid esters, dialkyl phosphate amines and the like, which are obtained by polymerizing ethylene oxide and propylene oxide, alkyl sulfate salts (such as sodium lauryl sulfate), and alkyl sulfonate salts. (Sodium 2-ethylhexene sulfonate, etc.), aryl sulfonates (sodium lignin sulfonate, sodium dodecylbenzene sulfonate, etc.)
Is mentioned. The content of the compound of the general formula (I) in the herbicide according to the present invention varies depending on the form of preparation, but is usually 1 to 20% by weight for powder and 20 to 6 for wettable powder.
0% by weight, 1-30% by weight for granules, 1-50% for emulsions
%, 10 to 50% by weight for the flowable preparation, and 20 to 90% by weight for the dry flowable preparation. The content of the adjuvant is 0 to 80% by weight, and the content of the carrier is 10%.
It is the amount obtained by subtracting the contents of the active ingredient compound and the adjuvant from 0% by weight.

The herbicide according to the present invention can be used for treating flooded soil,
It is effective in all treatment methods such as soil treatment, soil mixed layer treatment, foliage spraying treatment, and can be used in a wide range of 0.01 kg to 10 kg / ha as an active ingredient as an application rate. Is preferably used in the range of 0.05 kg / ha to 5 kg / ha.

The herbicide of the present invention can be used by mixing with one or more other herbicides, pesticides such as insecticides and plant growth regulators, soil conditioners or fertilizers. However, it is also possible to prepare a mixed preparation with these, and a synergistic effect can be expected in some cases. In this case, it is particularly advantageous to use it as a mixture with other herbicides.

Other herbicides include, for example, phenoxyacetic acid herbicides, benzoic acid herbicides, chlorinated carboxylic acid herbicides, carbamate herbicides, urea herbicides, sulfonylurea herbicides, acid amide herbicides. Herbicides, heterocyclic herbicides (triazine herbicides, diazine herbicides, etc.), phenolic herbicides, diphenyl ether herbicides, dipyridinium herbicides, dinitroaniline herbicides, organophosphate herbicides, Examples include phosphorus-containing amino acid herbicides, imidazolidinone herbicides, pyridine herbicides, quinoline herbicides, sulfonamide herbicides, cyclohexanone herbicides, other organic herbicides, and inorganic herbicides.

[0040]

Next, the present invention will be described in more detail by way of examples. First, as reference examples, general formulas (II) and (III)
And Preparation Examples of the compounds contained in (IX). Reference Example 1 Methyl 5-deoxy-5-C-methyl-3-O- (2
-Methylbenzyl) -D-xylofuranoside 5-Deoxy-1,2-O-isopropylidene-5-C
-Methyl-3-O- (2-methylbenzyl) -α-D-
70.97 g of xylofuranose was dissolved in methanol (300 m
After dissolving in 1), 0.5 g of p-toluenesulfonic acid was added.
Was added and the mixture was heated under reflux for 10 hours. After cooling, the reaction solution was neutralized with an aqueous sodium hydrogen carbonate solution, and the solvent was distilled off under reduced pressure.
This was added to water, extracted with a mixed solvent of ether and ethyl acetate (1: 1), and the organic layer was washed with water. This was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain an oily crude product. This was purified by silica gel chromatography (developing solvent; n-hexane: ethyl acetate = 3: 1) to obtain 64.21 g of the desired compound as an anomeric mixture of α-form and β-form. (Yield 99.2%) The anomeric mixture of α-form and β-form obtained here is precisely purified by silica gel chromatography (developing solvent; n-hexane: ethyl acetate = 5: 1) to obtain α And β-isomers.

Reference Example 2 Production of methyl 5-deoxy-2-O- (2-methoxymethylbenzyl) -5-C-methyl-3-O- (2-methylbenzyl) -D-xylofuranoside Obtained in Reference Example 1. 25.0 g of methyl 5-deoxy-5-C-methyl-3-O- (2-methylbenzyl) -D-xylofuranoside was dissolved in 200 ml of tetrahydrofuran, and 4.44 g of oily sodium hydride (liquid paraffin 40) was stirred. % Containing product) was gradually added. 1.0 g of tetrabutylammonium iodide and 22.2 g of (2-methoxymethyl) benzyl bromide were added thereto, and the mixture was stirred at room temperature for 4 hours. After adding a small amount of water under ice cooling, the solvent was distilled off under reduced pressure, and the obtained crude product was added to water and extracted with ether. The organic layer was sufficiently washed with water and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain an oily crude product.
The crude product was subjected to silica gel chromatography (developing solvent; n
-Hexane: ethyl acetate = 10: 1)
34.7 g of the target compound was obtained as an anomeric mixture of α-form and β-form. (Yield 92.4%)

Reference Example 3 1-O-acetyl-5-deoxy-5-C-methyl-2
-O- (2-methoxymethylbenzyl) -3-O- (2
Preparation of -methylbenzyl) -D-xylofuranose Methyl 5-deoxy-2- obtained by Reference Example 2
4.00 g of O- (2-methoxymethyl) benzyl-5-C-methyl-3-O- (2-methylbenzyl) -D-xylofuranoside was added to 15 ml of acetic acid and 3.5 ml of acetic anhydride.
And 0.75 ml of concentrated sulfuric acid was added under ice-cooling. After 12 hours at room temperature, the mixture was poured into ice water and extracted with chloroform. The organic layer was washed with water, a saturated aqueous solution of sodium hydrogencarbonate and saturated saline, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain an oily crude product. The crude product was purified by silica gel chromatography (developing solvent; n-hexane: ethyl acetate = 3: 1) to obtain 3.92 g of the desired compound as an anomeric mixture of α-form and β-form. (Yield 91.7%)

Reference Example 4 (2R, 3S, 3aS, 9bR) -2-ethyl-3-
(2-methylbenzyloxy) -6-chloromethyl-
3,3a, 5,9b-tetrahydro-2H-furo [3,3
Production of 2-c] [2] benzopyran 1) Methyl 2-O- (2-chloromethylbenzyl)-
Production of 5-deoxy-5-C-methyl-3-O- (2-methylbenzyl) -D-xylofuranoside Methyl 5-deoxy-5-C-methyl-3-O- (2- 2.5 g of (methylbenzyl) -D-xylofuranoside was dissolved in 15 ml of dimethylformamide, and 0.44 g of sodium hydroxide was added with stirring.
1.81 g of α, α′-dichloro-o-xylene was added thereto, and the mixture was stirred at 40 ° C. for 5 hours. The crude product obtained by performing the same post-treatment as in Reference Example 2 was subjected to silica gel chromatography (developing solvent; n-hexane: ethyl acetate = 1).
Purification was carried out by 0: 1) to obtain 3.50 g of the target compound as an anomeric mixture of α-form and β-form. (Yield 92.
0%) 2) (2R, 3S, 3aS, 9bR) -2-ethyl-3
-(2-methylbenzyloxy) -6-chloromethyl-
3,3a, 5,9b-tetrahydro-2H-furo [3,3
2-c] [2] Preparation of benzopyran Methyl 2-O- (2-chloromethylbenzyl) -5-deoxy-5-C-methyl-3- obtained by 1)
1.02 g of O- (2-methylbenzyl) -D-xylofuranoside was dissolved in 12 ml of chloroform, and 8.17 m of titanium tetrachloride (1.0 M solution in dichloromethane) was added under ice cooling.
1 was added. After stirring at room temperature for 2 hours, the mixture was poured into a saturated aqueous sodium hydrogen carbonate solution containing ice. The organic layer was sufficiently washed with water and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain an oily crude product. The crude product was subjected to silica gel chromatography (developing solvent; n-hexane:
Purification was performed using ethyl acetate = 5: 1) to obtain the desired compound 1.
00 g were obtained. (Yield 97.6%)

Next, Production Examples of the compound of the present invention represented by the general formula (I) will be described as Examples. Example 1 (2R, 3S, 3aS, 9bR) -2-ethyl-6-methoxymethyl-3- (2-methylbenzyloxy)-
3,3a, 5,9b-tetrahydro-2H-furo [3,3
Production of 2-c] [2] benzopyran (compound number 1 of general formula (I)) Methyl 5-deoxy-2- obtained by Reference Example 2
0.62 g of O- (2-methoxymethylbenzyl) -5-C-methyl-3-O- (2-methylbenzyl) -D-xylofuranoside (a mixture of α and β forms) was added to acetonitrile 1
The solution was dissolved in 0 ml, and 4.97 ml of tin tetrachloride (1.0 M solution in dichloromethane) was added under ice-cooling. After stirring at room temperature for 3 hours, the mixture was poured into a saturated aqueous solution of sodium hydrogencarbonate containing ice. The organic layer was sufficiently washed with water and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain an oily crude product. The crude product was purified by silica gel chromatography (developing solvent; n-hexane: ethyl acetate = 5: 1) to obtain 0.56 g of the desired compound. (Yield 98.5
%)

Example 2 (2R, 3S, 3aS, 9bR) -6-chloromethyl-
2-ethyl-3- (2-methylbenzyloxy) -3,
3a, 5,9b-Tetrahydro-2H-furo [3,2-
c] [2] Preparation of benzopyran (compound No. 1 of general formula (I)) 1-O-acetyl-5-deoxy-5-C-methyl-2-O- (2-methoxy) obtained by Reference Example 3 0.51 g of methylbenzyl) -3-O- (2-methylbenzyl) -D-xylofuranose was added to 1,2-dichloroethane 1
The solution was dissolved in 0 ml, and 0.55 g of aluminum chloride was added under ice cooling. After stirring at room temperature for 3 hours, the mixture was poured into a saturated aqueous solution of sodium hydrogencarbonate containing ice. The organic layer was sufficiently washed with water and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain an oily crude product. The crude product was purified by silica gel chromatography (developing solvent; n-hexane: ethyl acetate = 5: 1) to obtain 0.41 of the desired compound.
g was obtained. (Yield 93.5%)

Example 3 (2R, 3S, 3aS, 9bR) -2-ethyl-3-
(2-methylbenzyloxy) -6-formyl-3,3
a, 5,9b-Tetrahydro-2H-furo [3,2-
c] [2] Preparation of benzopyran (compound No. 2 of general formula (I)) A solution of 0.4 g of 2-nitropropane in methanol (15 m
0.81 g of sodium methoxide was added to 1) under ice cooling, and the mixture was stirred at room temperature for 30 minutes, and then obtained in Reference Example 4 (2R,
3S, 3aS, 9bR) -2-ethyl-6-chloromethyl-3- (2-methylbenzyloxy) -3,3a,
5,9b-tetrahydro-2H-furo [3,2-c]
[2] A solution of 1.5 g of benzopyran in methanol (15 m
l) was added and the mixture was refluxed for 3 hours. The reaction is concentrated under reduced pressure,
Water was added to the obtained residue and extracted with dichloromethane. The organic layer was sufficiently washed with water and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain an oily crude product. The crude product was purified by silica gel chromatography (developing solvent; n-hexane: ethyl acetate = 10: 1) to obtain 1.22 g (yield 87%) of the target compound.

Example 4 (2R, 3S, 3aS, 9bR) -2-methyl-3-
(2-methylbenzyloxy) -6- (1-hydroxyethyl) -3,3a, 5,9b-tetrahydro-2H-
Preparation of Furo [3,2-c] [2] benzopyran (Compound No. 3) (2R, 3S, 3aS, 9b) obtained by Example 3
R) -2-Ethyl-3- (2-methylbenzyloxy)
-6-formyl-3,3a, 5,9b-tetrahydro-
0.6 g of 2H-furo [3,2-c] [2] benzopyran
Was dissolved in tetrahydrofuran (10 ml), and 3.40 ml of methylmagnesium bromide (1.0 M solution in tetrahydrofuran) was added dropwise under ice cooling. After stirring at room temperature for 1 hour, the mixture was poured into ice-cooled diluted hydrochloric acid and extracted with ethyl acetate. The organic layer was washed with water and then with a saturated aqueous solution of sodium hydrogen carbonate, and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain an oily crude product. The crude product was purified by silica gel chromatography (developing solvent; n-hexane: ethyl acetate = 5: 1) to obtain 0.48 g (yield: 77.4%) of the target compound.

Example 5 (2R, 3S, 3aS, 9bR) -2-ethyl-3-
(2-methylbenzyloxy) -6-carboxy-3,
3a, 5,9b-Tetrahydro-2H-furo [3,2-
c] [2] benzopyran (compound number 1 of general formula (I)
Production of 5) (2R, 3S, 3aS, 9b) obtained by Example 3
R) -2-Ethyl-3- (2-methylbenzyloxy)
-6-formyl-3,3a, 5,9b-tetrahydro-
2H-Flo [3,2-c] [2] benzopyran 1.22
1.6 g of Jones' reagent in ice-cold acetone solution
Was added and stirred at room temperature for 2 hours. The reaction solution was concentrated under reduced pressure, and the obtained residue was dissolved in 2N sodium hydroxide solution and washed with ethyl acetate. The aqueous layer was made acidic with hydrochloric acid and extracted with hexane: ethyl acetate = 4: 1. The organic layer was sufficiently washed with water and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain an oily crude product. The crude product was purified by flash chromatography (FC-40, developing solvent; n-hexane: ethyl acetate = 6: 1) to obtain 1.11 g (yield: 87%) of the target compound.

The compounds of the general formula (I) prepared in the same manner as in Examples 1 to 5 are shown in Table 1 (Tables 1 to 9). In addition, their physical property values are shown in Table 2 (Tables 10 to 28).

[0050]

[Table 1]

[0051]

[Table 2]

[0052]

[Table 3]

[0053]

[Table 4]

[0054]

[Table 5]

[0055]

[Table 6]

[0056]

[Table 7]

[0057]

[Table 8]

[0058]

[Table 9]

[0059]

[Table 10]

[0060]

[Table 11]

[0061]

[Table 12]

[0062]

[Table 13]

[0063]

[Table 14]

[0064]

[Table 15]

[0065]

[Table 16]

[0066]

[Table 17]

[0067]

[Table 18]

[0068]

[Table 19]

[0069]

[Table 20]

[0070]

[Table 21]

[0071]

[Table 22]

[0072]

[Table 23]

[0073]

[Table 24]

[0074]

[Table 25]

[0075]

[Table 26]

[0076]

[Table 27]

[0077]

[Table 28] Next, formulation examples of the herbicide according to the present invention and herbicidal activity test examples will be described. Formulation Example 1 (Wettable powder) Compound (1) of the present invention: 20 parts by weight, neoperex (trade name, manufactured by Kao; sodium dodecylbenzenesulfonate): 2 parts by weight, Neugen EA80 (trade name, manufactured by Daiichi Kogyo Seiyaku) Polyoxyethylene nonylphenyl ether): 1 part by weight, 10 parts by weight of white carbon, and 67 parts by weight of diatomaceous earth were sufficiently pulverized and mixed to obtain a wettable powder.

Formulation Example 2 (Wettable powder) Compound (6) of the present invention: 20 parts by weight, sodium alkylbenzenesulfonate: 2 parts by weight, polyoxyethylene alkylphenyl ether: 1 part by weight, white carbon: 10 parts by weight, and Sieg Light: 67 parts by weight was well pulverized and mixed to obtain a wettable powder.

Formulation Example 3 (Wettable powder) Compound (3) of the present invention: 50 parts by weight, white carbon:
30 parts by weight, ammonium polyoxyethylene alkylphenyl ether sulfate: 6 parts by weight, sodium ligninsulfonate: 2 parts by weight, and diatomaceous earth: 12 parts by weight were thoroughly pulverized and mixed to obtain a wettable powder.

Formulation Example 4 (Floable agent) Compound (21) of the present invention: 5 parts by weight, sodium ligninsulfonate: 2 parts by weight, polyoxyethylene alkylaryl ether: 1 part by weight, water: 91.7 parts by weight Was added and mixed, and the mixture was pulverized using a sand grinder, and then 0.3 parts by weight of xanthan gum was added to obtain a flowable agent.

Formulation Example 5 (Floable agent) Compound (24) of the present invention: Sun extract P252 dissolved in 30 parts by weight of water and 50 parts by weight of water (trade name, as described above): 1
0 parts by weight were wet-pulverized and mixed, and then dissolved in 9.6 parts by weight of water, Kelzan S (trade name, manufactured by Kelco; xanthan gum): 0.2 part by weight and Deltop (trade name, manufactured by Takeda Pharmaceutical: organic iodine) 0.2 parts by weight were added and mixed to obtain a flowable agent.

Formulation Example 6 (Powder) Compound (29) of the present invention: 1 part by weight, Emulgen 910
(Trade name, manufactured by Kao; polyoxyethylene nonyl phenyl ether): 0.5 part by weight and kaolin clay: 9
8.5 parts by weight were pulverized and mixed well to obtain a powder.

Formulation Example 7 (Powder) Compound (33) of the present invention: 3 parts by weight, sodium ligninsulfonate: 3 parts by weight, polyoxyethylene alkylaryl ether: 2 parts by weight, and clay: 92 parts by weight were mixed and pulverized. A powder was obtained.

Formulation Example 8 (Water-dispersible granules) Compound (47) of the present invention: 55 parts by weight, toxanone 60P
N: 5 parts by weight, polyoxyethylene alkyl aryl ether: 5 parts by weight, and white carbon: 35 parts by weight are mixed well, then an appropriate amount of water is added to wet, and then extruded by a horizontal extrusion granulator. did. This is 30-60
After drying at 0 ° C and crushing, the granules were refined to 0.3 to 0.5 mm with a sizing machine to obtain a wettable powder for granules.

Formulation Example 9 (Granules) Compound (50) of the present invention: 3.0 parts by weight, Neoperex (trade name, as described above): 2 parts by weight, Sun extract P25
2 (trade name, manufactured by Sanyo Kokusaku Pulp; sodium ligninsulfonate): 2 parts by weight, 70.0 parts by weight of bentonite and 23 parts by weight of talc were mixed well, and then an appropriate amount of water was added to wet the mixture. And extruded by a horizontal extrusion granulator. This was air-dried at 30 to 60 ° C. and crushed, and then sized with a sizing machine to 0.3 to 1 mm to obtain granules.

Formulation Example 10 (granules) 0.5 part by weight of compound (53) of the present invention, gohsenol (G
osenol) GL-05s (PV from Nippon Gohsei)
A): 2 parts by weight, sun extract P252 (sodium lignin sulfonate manufactured by Sanyo Kokusaku Pulp): 2 parts by weight and clay:
After 95.5 parts by weight were mixed well, an appropriate amount of water was added to make it wet, and then extruded and granulated by a horizontal extrusion granulator.
This was air-dried at 60 to 90 ° C. and crushed.
A granule was obtained by sizing to 3 to 1 mm.

Formulation Example 11 (Emulsion) Compound (56) of the present invention: 10 parts by weight, Solpol 800
A (trade name, manufactured by Toho Chemical; a mixture of a nonionic surfactant and an anionic surfactant): 10 parts by weight and o-xylene: 80 parts by weight were mixed and dissolved to obtain an emulsion.

Formulation Example 12 (Wettable powder) Compound (73-A) of the present invention: 20 parts by weight, sodium alkylbenzenesulfonate: 2 parts by weight, polyoxyethylene alkylphenyl ether: 1 part by weight, white carbon: 15 parts by weight And Sigleite: 62 parts by weight were pulverized and mixed well to obtain a wettable powder.

Formulation Example 13 (Wettable powder) Compound (67) of the present invention: 50 parts by weight, white carbon: 30 parts by weight, ammonium polyoxyethylene alkyl phenyl ether sulfate: 6 parts by weight, sodium lignin sulfonate: 2 parts by weight And diatomaceous earth: 12 parts by weight were pulverized and mixed well to obtain a wettable powder.

Formulation Example 14 (oil-in-water emulsion EW) Compound (77) of the present invention: 5 parts by weight, toxanone FW-1
0 (trade name, manufactured by Sanyo Chemical Industries; polymer-based anion): 4
Parts by weight, xanthan gum: 0.3 parts by weight, Deltop:
88.5 parts by weight of water was added to 0.2 parts by weight and 2 parts by weight of polyoxyethylene alkylaryl ether, and emulsified by a homomixer to obtain an oil-in-water emulsion EW.

Formulation Example 15 (oil in water type emulsion EW) Compound (84) of the present invention: 30 parts by weight, Gohsenol KH
-20 (trade name, manufactured by Nippon Synthetic Chemical Co .; protective colloid formation): 4 parts by weight, xanthan gum: 0.3 part by weight, Deltop (trade name, Takeda Pharmaceutical: organic iodine-based fungicide): 0.2 61.5 parts by weight of water was added to 4 parts by weight of the polyoxyethylene alkylaryl ether and 4 parts by weight of the polyoxyethylene alkylaryl ether, and the mixture was wet-pulverized and mixed to obtain an oil-in-water emulsion EW.

Formulation Example 16 (Water-dispersible granules) Compound of the present invention (113): 50 parts by weight, toxanone 60
After well mixing PN: 5 parts by weight, polyoxyethylene alkylaryl ether: 5 parts by weight and white carbon: 40 parts by weight, an appropriate amount of water is added and wetted, and then extruded by a horizontal extrusion granulator. did. This is 30-6
After drying and crushing at 0 ° C., 0.3-0.5 mm
The resulting powder was granulated to give a wettable powder.

Formulation Example 17 (granules) Compound (119) of the present invention: 3.0 parts by weight, neoperex (trade name, as described above): 2 parts by weight, sun extract P2
52 (trade name, manufactured by Sanyo Kokusaku Pulp; sodium ligninsulfonate): 2 parts by weight, bentonite: 70.0 parts by weight, and talc: 23 parts by weight were mixed well, and then an appropriate amount of water was added to wet the mixture. And extruded by a horizontal extrusion granulator. After air-drying and crushing this at 30-60 ° C,
The mixture was sized to 0.3 to 1 mm with a sizing machine to obtain granules.

Formulation Example 18 (granules) Compound (122) of the present invention: 1.0 part by weight, Gosenol GL-05s (PV manufactured by Nippon Synthetic Chemical Co., Ltd.)
A): 2 parts by weight, sun extract P252 (sodium lignin sulfonate manufactured by Sanyo Kokusaku Pulp): 2 parts by weight and clay:
After 95.0 parts by weight were mixed well, an appropriate amount of water was added to wet the mixture, and the mixture was extruded and granulated by a horizontal extrusion granulator.
This was air-dried at 60 to 90 ° C. and crushed.
A granule was obtained by sizing to 3 to 1 mm.

Test Example 1 Flooded Soil Treatment Test (Pretreatment before Occurrence) Soil was packed in a 1/5000 arel wagner pot, and seeds of red snapper, oak, firefly and azalea were sown and flooded. Rice seedlings (2-
Two strains were used as one strain, and the two strains were transplanted and grown in a greenhouse. One day later (before weed development), the test compound
A treatment with a predetermined amount of granules (prepared according to the method described in Formulation Example 9) so that the dose becomes Kg / ha, and
On day 0, the occurrence of weeds and the status of phytotoxicity on rice were observed and investigated. The results are shown in Table 3 (Tables 29 to 31).

In the table, the degree of damage to the test plant and the degree of chemical damage to the crop are indicated by the following criteria in comparison with the case where the growth state of the plant is untreated. Indication Growth rate (%) 50 to 5 (dead) 46 to 10 (destructive) 3 11 to 40 (moderate damage) 241 to 70 (small damage) 171 to 70 90 (slightly harmful) 0 91-100 (harmless)

[0097]

[Table 29]

[0098]

[Table 30]

[0099]

[Table 31]

Test Example 2 Flooded Soil Treatment Test (Growth Season Treatment) Soil was packed in a 1/5000 arel wagner pot, and seeds of red snapper, oak, firefly, and azalea were sown and flooded. Rice seedlings (2-
Two strains were used as one strain, and the two strains were transplanted and grown in a greenhouse. When the millet becomes two leaves, the test compound becomes 3
A predetermined amount of granules (prepared according to the method described in Formulation Example 9) was treated so as to have a dosage of Kg / ha, and after 30 days, the occurrence of weeds and the state of phytotoxicity to rice were observed and investigated. The results are shown in Table 4 (Tables 32-35). In the table, the degree of damage to the test plant and the degree of
The display was the same as in Test Example 1.

[0101]

[Table 32]

[0102]

[Table 33]

[0103]

[Table 34]

[0104]

[Table 35]

Test Example 3 Upland soil treatment test (pre-emergence treatment) A 1/2500 arel resin pot was filled with soil, and this was filled with barnyardgrass, crabgrass, enokorogusa, chickweed, aobiu,
The soil mixed with soybeans and cotton seeds was covered with a soil of 1 to 2 cm, and grown in a greenhouse. One day later (before the emergence of weeds), a predetermined amount of wettable powder (prepared according to the method described in Formulation Example 1) was diluted with water so that the test compound had a dosage of 3 kg / ha, and 1 A spraying liquid amount equivalent to 10 L per are was sprayed uniformly on the soil surface using a pressurized micro sprayer. Thirty days after the application of the chemical, the growth of the weed and the phytotoxicity of the crop were observed and investigated. The results are shown in Table 5 (Table 3).
6-39). In the table, the degree of damage to the test plant and the degree of phytotoxicity to the crop are indicated in the same manner as in Test Example 1.

[0106]

[Table 36]

[0107]

[Table 37]

[0108]

[Table 38]

[0109]

[Table 39]

Test Example 4 Upland Field Foliage Treatment (Growing Season Treatment) A 1/1000 ares resin pot was filled with soil, and this was filled with barnyardgrass, crabgrass, enokorogusa, chickweed, aobiu,
Soybeans and cotton were sown one by one and grown in a greenhouse. When each plant has 2-3 leaves, the test compound is 3 kg / ha.
A predetermined amount of a wettable powder (prepared according to the method described in Formulation Example 2) was diluted with water and adjusted to have a dosage of 1
Spraying was uniformly performed using a pressurized micro atomizer at a spraying liquid amount equivalent to 10 L per are. Thirty days after the application of the chemical, the growth of the weed and the phytotoxicity of the crop were observed and investigated. The results are shown in Table 6 (Tables 40 to 42). In the table, the degree of damage to the test plant and the degree of phytotoxicity to the crop are indicated in the same manner as in Test Example 1.

[0111]

[Table 40]

[0112]

[Table 41]

[0113]

[Table 42]

[0114]

The compound of the present invention represented by the general formula (I) is a novel compound having a furobenzopyran ring,
As is clear from the above-mentioned test examples, it shows excellent herbicidal activity and selectivity. That is, when the compound of the present invention is used in a paddy field, it has excellent selectivity for paddy rice and shows a high herbicidal effect against important weeds such as foxtails, puppies, fireflies and azaleas. In addition, the compound of the present invention, soybeans in the field crops,
It has high selectivity for crops such as cotton, and
It shows a high herbicidal effect on important weeds such as Enochorogosa, Chickweed and Aobeyu. Therefore, the compound of the present invention can be applied as a paddy and upland herbicide.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI A01N 57/16 101 A01N 57/16 101Z // C07M 7:00 (72) Inventor Sadafumi Eda 1144 Togo, Mobara City, Chiba Prefecture Mitsui Higashi (72) Inventor Yasunaga Iwasaki 1144 Togo, Mobara-shi, Chiba Investigator, Mitsui Toatsu Chemicals Co., Ltd.Seiko Tamura (58) Field surveyed (Int.Cl. ⁷ , DB name) C07D 493/04 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A compound of the general formula (I)[Where R₁ Represents a lower alkyl group;_Two Is lower alk
Group, lower alkoxy group, halogen atom or halogen
Represents a substituted lower alkyl group;_Three Is lower alkyl group, lower
Lower alkoxy group, halogen atom, halogen-substituted lower alkyl
Represents a kill group, a phenoxy group or a benzyloxy group,
R_Four Represents a hydrogen atom or a lower alkyl group;_Five Ha
Ano group, nitro group, phenyl group, group -S (O)_qR₆ ,
Group-0S0_TwoR₆ , Group -XC (= O) R₆ , Group -XR
₇ , A group -XCH (R₉) C (= O) R₈, Group -XP (=
X) (XR₆)_Two, Group -N (R₉) R_Ten, Group -N (R₉) C
(= X) R ₁₁, Group -N (R₉) SO_TwoR₆, Group -C (R₉)
_TwoOR_Ten, Group -CH (R₉) S (O) _qR₆, Group -CH (R
₉ ) XC (= 0) R₁₁, Group -CH (R₉) N (R₉)
R_Ten, Group -CH (R₉) N (R₉) C (= X) R₁₁, Group-
CH (R₉) XP (= X) (XR₆)_Two , Group -C (= X)
R₈, Group -CH (XR₁₂) XR₁₃, Group -C (= X) N
(R_{1 Four}) R₁₅, Group -CH = NR₈ , Group -CH = CR₁₆R
₁₇, Group -O ｛C (R₁₈)_Two｝_r-O- (next to the benzene ring
Join the combined carbon atoms to form a 5- or 6-membered ring)
Or a group-｛C (R₁₈)_Two｝_s-(Adjacent on the benzene ring
Linking carbon atoms to form a 5- or 6-membered ring)
ＲR in the formula₆ Is a lower alkyl group or a (lower alkyl group,
May be substituted with a lower alkoxy group or a halogen atom)
Represents a phenyl group;₇ Is hydrogen atom, halogen substituted lower
Represents an alkyl group or an alkoxyalkyl group,₈ Is
Hydrogen atom, hydroxy group, lower alkyl group, lower alcohol
Xy, lower alkylthio or phenoxy groups
Then R₉ Represents a hydrogen atom or a lower alkyl group;_Ten
Is a hydrogen atom, lower alkyl group, halogen-substituted lower alkyl
Represents an alkyl group or an aralkyl group;₁₁Is lower alkyl
Group, halogen-substituted lower alkyl group, (lower alkyl group,
May be substituted with a lower alkoxy group or a halogen atom)
Phenyl group, lower alkoxy group, phenoxy group, lower
Represents a alkylamino group or anilino group;₁₂, R₁₃Is
A hydrogen atom or a lower alkyl group or R₁₂And R
₁₃Are cyclized together and-(CH_Two)_Two-Or-(CH
_Two)_Three-Represents R₁₄Represents a hydrogen atom or a lower alkyl group
Represents, R₁₅Is hydrogen atom, lower alkyl group, (lower alkyl
Even when substituted with a halogen group, a lower alkoxy group, or a halogen atom.
Good) phenyl group or R₁₄And R₁₅Together with oxygen
Atoms which may contain atoms, sulfur atoms or nitrogen atoms
Or a 6-membered ring,₁₆Is hydrogen atom, cyano group or low
Represents a lower alkoxycarbonyl group; ₁₇Is a hydrogen atom, low
Lower alkyl group, nitro group, cyano group or lower alkoxy
Represents a cyclocarbonyl group;₁₈Is hydrogen atom, lower alkyl
X represents an oxygen atom or a sulfur atom
Represents an atom, q is an integer of 0 to 2, r is 1 or 2,
s represents 3 or 4. ｝ M is an integer of 0 to 4 and n is 0
And p represents an integer of 1 to 3, m, n and
When p is 2 or more, R_Two , R_Three And R_Five Are the same for each
But they may be different. ]
Derivatives. 2. A compound represented by the general formula (I):[Where R₁ Represents a lower alkyl group;_Two Is lower alk
Group, lower alkoxy group, halogen atom or halogen
Represents a substituted lower alkyl group;_Three Is lower alkyl group, lower
Lower alkoxy group, halogen atom, halogen-substituted lower alkyl
Represents a kill group, a phenoxy group or a benzyloxy group,
R_Four Represents a hydrogen atom or a lower alkyl group;_Five Ha
Ano group, nitro group, phenyl group, group -S (O)_qR₆ ,
Group-0S0_TwoR₆ , Group -XC (= O) R₆, Group -XR₇,
The group -XCH (R₉) C (= O) R₈, Group -XP (= X)
(XR₆)_Two, Group -N (R₉) R_Ten, Group -N (R₉) C (=
X) R₁₁, Group -N (R₉) SO_TwoR₆ , Group -C (R₉)_TwoO
R_Ten, Group -CH (R₉) S (O)_qR₆, Group -CH (R₉)
XC (= 0) R₁₁, Group -CH (R₉) N (R₉) R_Ten, Basis
-CH (R₉) N (R₉) C (= X) R₁₁, Group -CH (R
₉) XP (= X) (XR₆) _Two , Group -C (= X) R₈ , Basis
-CH (XR₁₂) XR₁₃, A group -C (= X) N (R₁₄) R
₁₅, Group -CH = NR₈ , Group -CH = CR₁₆R₁₇, Group -O
｛C (R₁₈)_Two｝_r-O- (adjacent carbons on the benzene ring
Linking the atoms to form a 5- or 6-membered ring) or a group-
｛C (R₁₈)_Two｝_s-(Adjacent carbon atoms on the benzene ring
To form a 5- or 6-membered ring);
₆ Is a lower alkyl group or (lower alkyl group, lower alkyl
Phenyl, which may be substituted with a oxy group or a halogen atom)
R represents a group₇ Is a hydrogen atom, halogen-substituted lower alkyl
Or an alkoxyalkyl group,₈ Is hydrogen field
, Hydroxy group, lower alkyl group, lower alkoxy
A lower alkylthio group or a phenoxy group;
₉ Represents a hydrogen atom or a lower alkyl group;_TenIs hydrogen
Atom, lower alkyl group, halogen-substituted lower alkyl group
Or an aralkyl group;₁₁Is a lower alkyl group, halo
Gen-substituted lower alkyl group, (lower alkyl group, lower alkyl group
Phenyl, which may be substituted with a oxy group or a halogen atom)
Group, lower alkoxy group, phenoxy group, lower alkyl group
Represents a mino group or an anilino group;₁₂, R₁₃Are each
Hydrogen atom or lower alkyl group or R₁₂And R₁₃Together
And cyclized to-(CH_Two)_Two-Or-(CH_Two)_Three-
Represents, R₁₄Represents a hydrogen atom or a lower alkyl group;
₁₅Represents a hydrogen atom, a lower alkyl group, a (lower alkyl group,
A alkoxy group or a halogen atom)
Phenyl or R₁₄And R₁₅Together with oxygen atoms, sulfur
5 or 6 members which may contain yellow or nitrogen atoms
Represents a ring, R₁₆Is hydrogen atom, cyano group or lower alcohol
X represents a carbonyl group; ₁₇Is hydrogen atom, lower alkyl
Group, nitro group, cyano group or lower alkoxycarbo
Represents a phenyl group;₁₈Is a hydrogen atom, a lower alkyl group or
X represents a halogen atom, and X represents an oxygen atom or a sulfur atom.
Q is an integer of 0 to 2, r is 1 or 2, and s is 3
Or 4 ｝ M is an integer of 0-4, n is an integer of 0-2
And p represents an integer of 1 to 3, and m, n and p are 2 or more.
When above, R_Two , R_Three And R_Five Are the same but different
May be. Furbenzobenzopyran derivatives represented by the formula:
A herbicide comprising as an active ingredient.