JPS63267779A - Coumarin derivative, its production and herbicide containing said derivative as active component - Google Patents

Abstract

NEW MATERIAL:The coumarin derivative of formula I (R is lower alkyl). EXAMPLE:N-(7-fluoro-4-isopropyl-2-oxo-2H-benzopyran-6-yl)-3,4,5,6-tetr ahydroph thalimide. USE:An active component for herbicide. It exhibits excellent herbicidal effect against broad-leaved weeds such as cocklebur, common morning-glory and livid amaranth, gramineous weeds such as green fox tail, etc., by foliar treat ment and soil treatment, and gramineous weeds such as barnyard grass, cyperaceous weeds such as bulrush, broad-leaved weeds such as start wort and arrowhead, etc., by water treatment of paddy field and is free from phytotoxicity to main crops such as barley, cotton, corn and rice. PREPARATION:The compound of formula I can be produced by reacting 1 equivalent of an aminocoumarin derivative of formula II with 1.0-1.1 equivalent of 3,4,5,6-tetrahydrophthalic anhydride in the absence of solvent or in a solvent such as acetic acid at 70-120 deg.C for 1.0-10hr.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel marine derivative, a method for producing the same, and a herbicide containing the same as an active ingredient.

It has been known that various coumarin derivatives exist as plant components. However, there are almost no reports on coumarin derivatives having herbicidal activity.

As a result of various studies on coumarin derivatives having excellent herbicidal efficacy, the present inventors found that they have the general formula [wherein R represents a lower alkyl group]. It was discovered that the coumarin derivative represented by (hereinafter referred to as the compound of the present invention) is a compound having excellent herbicidal activity, leading to the present invention.

The compound of the present invention can be used to treat various weeds that are problematic in foliar and soil treatments in upland fields, such as freckle weeds, Japanese knotweed, purslane, chickweed, whiteweed, blue radish, Japanese daikon radish, Japanese radish, American hornwort, Ebisu grass, Japanese croaker, Japanese goldenrod, Field pansy, Yaemugura, American morning glory, Malva morning glory,
Against broad-leaved weeds such as Physalis spp., Physalis spp., Prunus marigold, and corn marigold, grass species weeds such as Japanese barnyard grass, Japanese millet grass, foxtail grass, black grass, sycamore, oats, oats, and Seiban sorghum, and weeds of the Asiatic family such as Asiatic dayflower. It has a herbicidal effect and does not cause any harmful effects on major crops such as corn, wheat, rice, divers, and cotton.

In addition, the compound of the present invention can be applied to various weeds that are problematic in the waterlogging treatment of rice fields, such as grass weeds such as Japanese millet, broad-leaved weeds such as azalea, commonweed, and Japanese chickweed, cyperaceae weeds such as bulrushes, and cypress grass. It has a herbicidal effect on grasses such as Prunus japonicus.

Next, a method for producing the compound of the present invention will be explained.

The compound of the present invention has the general formula (I[) [wherein R represents the same meaning as above]. It can be produced by reacting the aminocoumarin derivative represented by the following formula with 8,4,5゜6-titrahydrophthalic anhydride.

The reaction is usually carried out without a solvent or in a solvent, and when a solvent is used, a fatty acid such as acetic acid or propionic acid, water, etc., or a mixture thereof is usually used. The reaction temperature is usually 70
~120°C, the reaction time is usually in the range of 1.0 to 10 hours, and the amount of reagent used in the reaction is 8.4° per equivalent of the aminocoumarin derivative represented by general formula (II). 5.6-titrahydrophthalic anhydride is usually 1.0 to 1
．． 1 equivalent is used. After the reaction is complete, add water to the reaction solution,
By performing conventional treatments such as organic solvent extraction and concentration, and performing operations such as chromatography and recrystallization as necessary, the desired compound of the present invention can be obtained.

The compounds of the present invention produced by the above production method include:
For example, in general formula CI), R is a methyl group, an ethyl group,
Examples include compounds having an isopropyl group, an n-propyl group, an n-butyl group, an isobutyl group, a 5ea-butyl group, and the like.

General formula (
The aminocoumarin derivative represented by II) can be produced by the following route.

(1) (IT) (V)
[■] [■] [In the formula, R represents the same meaning as above, R' represents an alkoxymethyl group, and R' represents an alkyl group. ] That is, the 0-hydroxyphenylketone derivative represented by the general formula (II) is prepared at -5 to 10°C in the presence of a mineral acid such as sulfuric acid.
and nitric acid (generally d-1.5 is used).

) is used for nitration. The amount of reagent used in the reaction is usually 1.0 to 1.6 equivalents of nitric acid per equivalent of the 0-hydroxyphenylketone derivative represented by the general formula J]. Since the nitration reaction occurs at the O-position or p-position of the hydroxyl group, a mixture is produced, which can be separated by means such as column chromatography. The obtained nitrohydroxyphenylketone derivative represented by the general formula (mV) is heated to 10 to 10
By reacting with alkoxymethyl chloride or alkoxymethyl bromide at 0°C, a compound represented by general formula (V) is led to decay. The reaction is usually carried out using dimethylformamide, dimethylacetamide, dimethylsulfoxide,
The process is carried out in a solvent such as methanol or ethanol, and the amounts of reagents used are usually 1.0 to 1.1 equivalents of the base and 1.0 to 1.1 equivalents of the alkoxy phenyl ketone derivative represented by the general formula (IV). The amount of methyl chloride or alkoxymethyl bromide is 1.0 to 1.5 equivalents. Furthermore, the compound represented by the general formula (V) is prepared by the general formula [■] in the presence of a base such as sodium hydride or n-butyllithium [wherein R' represents the same meaning as above, and "is a lower alkyl group"] ] By reacting with a compound represented by the general formula (V
This leads to the cinnamic acid ester derivative represented by I). The reaction is usually carried out at 0 to 40°C in a solvent such as an aromatic hydrocarbon such as toluene or benzene, or an ether such as tetrahydrofuran, ethyl ether, or dimethoxyethane, and the amount of the reagent used is based on the general formula (V). The amount of the compound represented by the general formula [■] is 1.0 to 1.
1 equivalent, and the base is 1.0 to 1.2 equivalents.

Regarding the double bonds produced, this reaction usually gives a mixture of cis and trans forms, which can be used in the next reaction without separation. The cinnamate ester derivative represented by the general formula (VI) is led to the phenylpropionate ester derivative represented by the general formula [■] by a reduction method such as catalytic reduction. As a reduction method, for example, palladium, platinum, etc., is added in an alcohol such as ethanol to a concentration of 0.1~
A method using 10 mol% is mentioned. The phenylpropionic acid ester conductor represented by the general formula [Vo is 0.01
A ring-closing reaction is carried out in the presence of an acid such as sulfuric acid, hydrochloric acid, or hydrobromic acid in a mole % to large excess amount to lead to an aminocoumarin derivative represented by the general formula CII). The reaction is usually a metamail,
Alcohol such as ethanol, 1,4-dioxane,
The reaction is carried out in an ether such as 1.2-dimethoxyethane, an acid such as acetic acid or propionic acid, or a solvent such as water at a temperature from room temperature to the boiling point of the solvent.

After each reaction leading from the O-hydroxyphenylketone derivative represented by the above general formula (m) to the aminocoumarin derivative represented by the general formula (II), usual post-treatment is performed, and if necessary, chromatography etc. It is also possible to perform the following processing.

When using the compound of the present invention as an active ingredient of a herbicide,
It is usually mixed with solid carriers, liquid carriers, surfactants, and other formulation auxiliaries to formulate emulsions, wettable powders, suspensions, granules, and the like.

These preparations contain the compound of the present invention as an active ingredient in a weight ratio of 0.1 to 80%, preferably 1 to 70%.

Examples of solid carriers include fine powders or granules such as kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, walnut powder, urea, ammonium sulfate, and synthetic hydrous silicon oxide. Liquid carriers include aromatic hydrocarbons such as xylene and methylnaphthalene, alcohols such as isopropanol, ethylene glycol, and cellosolve, ketones such as acetone, cyclohexanone, and isophorone, vegetable oils such as soybean oil and cottonseed oil, and dimethyl sulfoxide. ,N,N
- Dimethylformamide, acetonitrile, water, etc.

Surfactants used for emulsification, dispersion, wetting, etc. include alkyl sulfate salts, alkyl sulfonate salts, alkylaryl sulfonate salts, dialkyl sulfosuccinate salts, polyoxyethylene alkylaryl ether phosphate salts, etc. Examples include anionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene polyoxypropylene block copolymer, sorbitan fatty acid ester, and nonionic surfactants such as polyoxyethylene sorbitan fatty acid ester. It will be done.

As formulation adjuvants, lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC
(carboxymethylcellulose), PAP (isopropyl acid phosphate), and the like.

The compound of the present invention is usually formulated and treated with soil, foliage, or flooding before or after the emergence of weeds. Soil treatment includes soil surface treatment, soil mixing treatment, etc., and foliage treatment includes treatment from above the plant body, as well as local treatment that treats only weeds so that they do not attach to crops.

When the compound of the present invention is used as an active ingredient of a herbicide, the treatment amount varies depending on weather conditions, formulation form, treatment time, method, location, target weeds, target crops, etc., but is usually 0 per are. .1P~100? , preferably 0.
51 to 50P, and emulsions, wettable powders, suspension agents, etc. are usually mixed with 1 liter to 10 liters of water per 1 are (adding auxiliary agents such as spreading agents if necessary). Granules and the like are usually processed as they are without any dilution.

In addition to the above-mentioned surfactants, the spreading agents include polyoxyethylene resin acid (ester), lignin sulfonate,
Examples include abietate, dinaphthylmethane disulfonate, and paraffin.

Hereinafter, the present invention will be explained in more detail with reference to production examples, formulation examples, and test examples, but the present invention is not limited to these examples.

First, a production example of the compound of the present invention will be shown.

Production example 1 6-amitwofluoro-4-isopropyl-2H-
Benzobilan-2-one 0.81 and 8°4.5.6-titrahydrophthalic anhydride 0.21? and acetic acid 10wt
The mixture was refluxed for 2 hours in a vacuum chamber. Next, water was added and the mixture was extracted with ethyl acetate. The organic layer was washed with water, then with saturated aqueous sodium bicarbonate, and dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: hexane-ethyl acetate mixed solvent) to obtain N-(7-fluoro-4-isopropyl-2-oxo-2H-benzobilane-6). -yl)-8,4°5.6-titrahydrophthalimide (hereinafter referred to as the compound (1) of the present invention) 0.4F was obtained as a glassy substance.

'H-NMR (deuterated chloroform solvent, TM8 internal standard)
δ value (PPm) 1.8 (6H, d) 1.8 (4H
, m) 2.45 (4H, m) 8.2 (IH, m) 6
．． 8 (IH, I) 7.18 (IH, d) 7.55
(IH,a) Production Example 2 6-ami2fluoro-4 was prepared in the same manner as in Production Example 1.
-Methyl-2H-benzobilan-2-one using N-
(7-fluoro-4-methyl-2-oxo-2H-benzobilan-2-yl)-8,4,5,6-titrahydrophthalimide (hereinafter referred to as the compound (2) of the present invention) in a glassy form obtained as.

'H-NMR (deuterated chloroform solvent, TM8 internal standard)
δ value (PPm) 1.85 (4H, m) 2.45 (7
H, m) 6.28 (IH, +1) 7.18 (IH,
d) 7.55 (IH, d) Next, the production of the raw material compound will be shown as a reference example.

Reference Example 1 Ten volumes of 4-fluoro-2-hydroxy-2'-methylpropiophenone were added to 50 ml of concentrated sulfuric acid at 0°C. Furthermore, add ice-cooled fuming nitric acid (d, 1.50) at 8.8F to
The mixture was added dropwise at θ°C, stirred for 80 minutes at 0°C, poured into ice water, and extracted with ether. The organic layer was washed with water, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography (eluent: hexane-ethyl acetate mixed solvent) to obtain 4-fluoro-2-hydroxy-5-nitro-2'-methylpropiophenone 4.
I got 1.

mp 59.9℃ 'H-NMR (deuterated chloroform solvent, TM8 internal standard)
δ value (PPm) 1.25 (6H, d) 8, +5 (
IH, ff1) 6.7 (IH, d) 8.55 (IH
, d) 18.25 (IH, bs) The nitrohydroxyphenylketone derivative represented by the general formula (ff) obtained in the same manner as above and its physical properties are shown below.

4-Fluoro-2-hydroxy-5-nitroacetophenone ff1P 96°C 4-fluoro-2-hydroxy-5-nitrobutyrophenone mP 80.4°C 4-fluoro-2-hydroxy-5-nitro8'-methylbutyrophenone mp 79.8°C Reference Example 2 Add 2.8 fP of sodium hydride (60% oily) to dimethylformamide 50+d, and add 4-fluoro-2
A solution of -hydroxy-6-nitro-2'-methylpropiophenone IIF in dimethylformamide 100- was added dropwise at -6 to 6°C. After the dropwise addition was completed, the mixture was stirred at 0°C until gas generation stopped, and then 2-chloromethyl methyl ether 4F was added at 0°C. Next, the mixture was stirred at room temperature for 1 hour and then at 40-50°C for 1 hour, poured into water, and extracted with ether. Dry the organic layer with magnesium sulfate,
The crystals obtained by distilling off the solvent under reduced pressure were washed with cold methanol to obtain 4-fluoro-2-methoxymethoxy-5-nitro-2'-methylpropiophenone tt, ay.

mP81.4℃ By the same operation as above, 4-fluoro-2-hydroxy-
4-Fluoro-2-methoxymethoxy-6-nitroacetophenone was obtained by using 4-fluoro-2-hydroxy-6-nitroacetophenone in place of 5-nitro-2'-methylpropiophenone.

mp94°C Reference Example 8 Sodium hydride (50% oil) 0.96F was added to tetrahydrofuran 80°C, and trimethylphosphonoacetate (8.6F) was added dropwise at 6 to 10°C. Stir at 10°C until no gas evolution is observed, then add 6.4P of 4-fluoro-2-methoxymethoxy-6-nitro-2'-methylpropiophenone to 100% of tetrahydrofuran.
A solution dissolved in - was added dropwise at 10 to 80°C. After the dropwise addition was completed, the mixture was stirred at room temperature for 1 hour, and further heated under reflux for 1 hour. Next, the mixture was allowed to cool to room temperature, and then water was added and extracted with ether. The organic layer was washed with water, dried over magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: hexane-ethyl acetate mixed solvent) to obtain β-(4-fluoro-2- Methyl methoxymethoxy-5-nitrophenyl)-β-isopropylacrylate 8
．． 1? Obtained 0 fnp92.2℃'H-NMR (deuterated chloroform solvent, TM8 internal standard)
δ value (PPm) 1.0 (6H, d) 8.4 (8H
, 9) 8.7 (8H, S) 4.0 (IH, m) 5.
2 (2H, S) 5.6 (IH, s) 7.05 (IH
, d) 7.75 (IH, d) Reference Example 4 β-(4-fluoro-2-methoxymethoxy-5-nitrophenyl)-β-isobrobyl methyl acrylate 1,
6f and 10% palladium carbon 100v ethanol 10
In addition to 0+gt, hydrogen gas was introduced at normal pressure and room temperature to perform a reduction reaction. After the reaction was completed, the solution was filtered and the solvent was distilled off under reduced pressure to obtain 1.4P of methyl 8-isopropyl-8-(5-amino-4-fluoro-2-methoxymethoxyphenyl)propionate.

Reference example 5 8-isopropyl-3-(5-amino-4-fluoro-
Methyl 2-methoxymethoxyphenyl)propionate 1
．． 4? was dissolved in methanol (20°), concentrated hydrochloric acid (10°) was added, and the mixture was heated under reflux for 4 hours. Next, water was added, methanol was distilled off under reduced pressure, and sodium hydroxide aqueous solution was added to adjust the pH.
= 5 and extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography to obtain 6-aminofluoro-4-isopropyl-2H-benzopyran-2-
On 0.4F was obtained.

ff1P 1 2 1-122℃ 'H-NMR (deuterated chloroform solvent, TM8 internal standard)
δ value (PPm) 1.8 (6H, d) 8.2 (I
H, m) 4.0-4.5 (2H, bs) 6.2 (I
H, 8) 6.98 (IH, d) 7.1 (IH, d)
An example of the aminocoumarin derivative represented by the general formula 1''U) obtained by #J1 as above is shown below.

6-aminofluoro-4-methyl-2H-benzopyran-2-one 6-aminofluoro-4-ethyl-2H-benzopyran-2-one 6-amino-7-fluoro-4-propyl-2H-benzopyran -2-one 6-adeno7-fluoro-4nibutyl-2H-benzopyran-2-one 6-ami2-fluoro-4-isobutyl-2H-benzopyran-2-one 6-ami2-fluoro-4-1ee- Butyl-2H
-Benzopyran-2-one Next, a formulation example will be shown. Parts represent parts by weight.

Formulation Example 1 50 parts of the compound of the present invention (2), 8 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and 46 parts of synthetic hydrous silicon oxide are thoroughly ground and mixed to obtain a wettable powder.

Formulation Example 2 6 parts of the compound of the present invention (1), 14 m of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate, 80 parts of xylene and 45 parts of cyclohexanone are thoroughly mixed to obtain an emulsion.

Formulation Example 8 2 parts of the compound of the present invention (2), 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignosulfonate, 80 parts of bentonite, and 66 parts of kaolin clay were thoroughly ground and mixed, and water was added and kneaded thoroughly. Granulate and dry to obtain granules.

Formulation Example 4 25 parts of the compound of the present invention (1), 8 parts of polyoxyethylene sorbitan monooleate, 8 parts of CMC, and 69 parts of water are mixed and wet-pulverized until the particle size becomes 6 microns or less to obtain a suspension.

Next, test examples demonstrate that the compounds of the present invention are useful as active ingredients of herbicides. Incidentally, coumarin represented by the formula (hereinafter referred to as compound symbol (A)) was used as a comparison control.

In addition, the herbicidal efficacy was determined by visual observation of the degree of inhibition of budding and growth of the test plants during the survey, and a score of 10 was given when there was no or almost no difference from when the test plant was not tested. Those whose growth is completely inhibited are evaluated on a scale of 6 from θ to 6, with a rating of 5 and a rating of 0.1.2.
．． 8.4.5.

Test Example 1 Upland Stem and Leaves Treatment Test A vat with an area of 88 x 2 Bcm and a depth of 110* was filled with upland soil, and sowed with Japanese Physalis, Marupa morning glory, Japanese sorghum, Japanese Physalis, Japanese commonweed, Japanese millet, and Seiban sorghum, and grown for 16 days. Then, make an emulsion of the test compound according to Formulation Example 2, dilute the specified amount with water equivalent to 6 liters per are containing a spreading agent, and apply it uniformly over the entire stem and leaf area from the top of the plant using a small sprayer. Processed. The growth conditions of weeds and crops differ depending on the grass species, but 1
At the ~4-leaf stage, the plant height was 2-12 sides. The herbicidal efficacy was investigated 20 days after the treatment. The results are shown in Table 1. Note that this test was conducted in a greenhouse throughout the entire period.

/' Table 1 Test Example 2 Field soil treatment test surface 13188 x 29 am", depth 11111 (7
) Field soil was filled in a vat, and soybean, cotton, corn, rice, Japanese radish, Japanese phyllocarp, Japanese sorghum, red deer, Seiban sorghum, and foxtail were sown in trays and loaded to a thickness of 1 to 2 υ.

The test compound was made into an emulsion according to Formulation Example 2, a predetermined amount of the emulsion was diluted with water equivalent to 10 liters per are, and the emulsion was applied to the broken earth surface using a small sprayer.

After treatment, the plants were grown in a greenhouse for 20 days and their herbicidal efficacy was investigated.

The results are shown in Table 2.

Table 2 Test Example 3 Paddy field flooding treatment test A cylindrical plastic pot with a diameter of 3 cm and a depth of 12,611 cm was filled with paddy soil, and the rice fields were filled with rice field soil,
Seeds of Kikashigusa, Chickweed) and Firefly were mixed in at a depth of 1 to 2 cm. After flooding the fields to create a paddy field, tubers of Urikawa were buried at a depth of 1 to 2 mm and grown in a greenhouse.

Six days later (at the beginning of each weed's emergence), the test compound was made into an emulsion according to Formulation Example 2, a predetermined amount of the emulsion was diluted with 5 milliliters of water, and the emulsion was applied to the water surface. After treatment, the plants were grown in a greenhouse for 20 days and their herbicidal efficacy was investigated. The results are shown in Table 8.

jI8 table

Claims (3)

[Claims] (1) General formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R represents a lower alkyl group. ] A coumarin derivative represented by. (2) General formula ▲ Numerical formula, chemical formula, table, etc. are available ▼ [In the formula, R represents a lower alkyl group. ] A general formula characterized by reacting an aminocoumarin derivative represented by 3,4,5,6-tetrahydrophthalic anhydride ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R is as above. express the same meaning. ] A method for producing a coumarin derivative. (3) General formula ▲ Numerical formula, chemical formula, table, etc. are available ▼ [In the formula, R represents a lower alkyl group. ] A herbicide characterized by containing a coumarin derivative represented by the following as an active ingredient.