JPH04145078A - Pyrroledicarboxylic acid derivative and herbicide - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I [R1 is H or (phenyl) lower alkyl; R2 is OH, lower alkyl, lower alkylthio or N(R4)R5 (R4 and R5 are H, lower alkyl or 2,6-diethylphenyl); R3 is pyridyl, thienyl, furyl or trifluoromethyl]. EXAMPLE:2-(3-Pyridyl)-5-phenyl-pyrrole-3,4-dicarboxylic acid dimethyl ester. USE:A herbicide. PREPARATION:An acetylenedicarboxylic acid ester derivative shown by formula II is reacted with an N-Acylphenylglycine derivative shown by formula III in an organic solvent such as preferably acetic anhydride at >=100 deg.C.

Description

[Detailed description of the invention] Purpose of invention Industrial applications The present invention relates to a novel pyrrolecarphonic acid conductor.

More specifically, the present invention relates to a herbicide characterized by containing a novel pyrrole dicarboxylic acid derivative represented by the general formula (I) below as an active ingredient. Therefore, the present invention is useful in the chemical industry, agriculture, and especially in the agricultural chemical manufacturing field.

BACKGROUND OF THE INVENTION Several compounds have been known that have chemical structures similar to those of formula (I) below.

For example, the following formula (II) compound or Ikiris Patent No. 21
Publication No. 94788, Formula (m) compound or Ikiris Patent No. 2
It is disclosed in Japanese Patent No. 21480, etc., and there is a description that these compounds have herbicidal activity.

Compounds of formula (II) (R and R' independently represent an alkenyl group, an alkynyl group, or a halogenated alkyl group; , mono- or dialkoxyalkyl group, difluorometholoxy group, alkylthio group, amino group, mono- or dialkylamino group,
A cyano group or a nitro group is represented, and R2 represents a hydrogen atom, a hydroxymethyl group, a dialkylboron group, an alkylcarbonyl group, an alkylcarbonyloxyalkyl group, an alkyloxycarbonylthio group, or a phenyloxycarbonylthio group. ) Compound of formula (m) (R and R1 each independently represent an alkyl group, a mono- or polyhalogenated alkyl group, an alkenyl group, an alkynyl group, A represents a C1-C3 alkyl group,
J represents a petro ring containing a nitrogen atom, R2 is a hydrogen atom,
Indicates a hydroxymethyl group, dialkylboron group, and alkylcarbonyl group. ) However, the pyrroldicarboxylic acid derivative of the present invention has not been described in any literature and is a new compound.

Problems to be Solved by the Invention Compounds 4 that are chemically structurally similar to the compounds of the present invention, such as 2-methyl-5-pyridylpyrrole carboxylic acid derivatives, are practical as herbicides in terms of herbicidal effects and phytotoxicity, as shown in the test examples below. The above is not necessarily satisfactory.

The object of the present invention is to provide a new herbicide having superior herbicidal activity and safety as a paddy rice herbicide and an upland herbicide in place of these known compounds.

Means for Solving the Constituent Problems of the Invention In order to achieve the above object, the present inventors synthesized a large number of pyrrole sicaphonic acids and conducted extensive studies on their usefulness. As a result, it was discovered that the pyrroldicarboxylic acid derivative described below is a new compound that has not been described in any literature, has high herbicidal activity and safety, and achieves the above objectives.

Therefore, the gist of the first invention is represented by the following general formula (I) (wherein R represents a hydrogen atom, a lower alkyl group, or a phenyl lower alkyl group, and R2 represents a hydroxyl group or a lower alkoxy group). , lower alkylthio group, optional hydrogen atom, lower alkyl group, 2,6-ethylphenyl group)
and R1 represents a pyridyl group, a thienyl group, a furyl group, or a trifluoromethyl group. ] It is a pyrroldicarboxylic acid derivative represented by

The alkyl group of the lower alkoxy group and the lower alkyl group may be linear or branched. Moreover, lower means carbon number 1-6.

Furthermore, the gist of the second invention is as follows:
A herbicide characterized by containing the pyrrole dicarboxylic acid derivative of I) as an active ingredient.

Next, the following examples and test examples are also referred to for typical effects of the compounds of the present invention of the general formula (I).

No. table i month The compound of general formula (1) of the present invention is a new compound.

The compound of general formula (I) acts as an active ingredient for controlling various weeds in paddy fields or upland fields.

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

Examples Manufacturing method of the compound of the present invention The first method of manufacturing the compound of general formula (I) according to the present invention can be carried out by the following three methods, namely, method (A), method (
B) or method (C).

Method (A) A compound (■)' in which R1, a hydrogen atom, and R2 is a lower alkoxy group in the general formula (I) is an acetylene dicarboxylic acid ester derivative represented by the general formula (TV), and the compound (■)' is represented by the general formula (V). It can be produced by reacting N-acylphenylchrysine derivatives.

(TV) (V) (In the formula, R3 is as defined above.) This cyclization reaction is usually carried out in an organic solvent. Usable solvents include hydrocarbons such as benzene, toluene and xylene, and carboxylic acid anhydrides such as acetic anhydride and propionic anhydride, with acetic anhydride being preferred. The reaction temperature is usually from room temperature to the boiling point of the solvent, preferably 10
The temperature is 0°C or higher.

After the reaction is completed, the compound of the present invention can be obtained by adding water and an organic solvent such as benzene, toluene, tetrahydrofuran, chloroform, etc. to separate the desired product and distilling off the solvent. Examples of production by this method are shown in Examples 1 and 2. Note that the compound of formula (IV), which is a starting material, is a known compound, and the compound of formula (V) is a known compound or a compound of known compound (Chem, Ber), Vol. 103, p. 2356-
It can be easily produced by reacting the corresponding carboxylic acid halide with phenylchrysine according to the production method described on page 2367 (1970).

Method (B) Compound (I) of general formula (I) where R1 is a lower alkyl group, phenyl lower alkyl group and R2 is lower alkoxy
can be produced by reacting the compound (I)' obtained in method (A) with a lower alkyl halide or a phenyl lower alkyl halide.

(I)'(I)'' (In the formula, R4 is the same as above, and X represents a halogen atom6) This reaction is usually carried out in an organic solvent. Examples of solvents that can be used include Hensen, toluene, Hydrocarbons such as hexane, ethers such as ethyl ether, dioxane, and tetrahydrofuran, esters such as methyl acetate and ethyl acetate, ketones such as acetone and methyl isophthyl ketone, acetonitrile, propionitrile, etc. Nitriles, dimethylformamide, dimethyl sulfoxide, etc.

As acid binders, inorganic bases such as sodium hydride and potassium carbonate, or organic bases such as triethylamine and lysine can be used.

The reaction can proceed at room temperature, or the reaction time can be shortened by humidifying the solvent up to its boiling point.

After the reaction is completed, water and an organic solvent such as Hensen, toluene, or tetrahydrofuran are added to separate the desired product, and the solvent is distilled off to obtain a compound of the present invention. Examples of production by method (B) are shown in Examples 3 and 4.

Method] Compound CI whose general formula (I) is R2, hydroxyl group, lower acetate) ' is method (A) or method (B)
After hydrolyzing the compound (1)' or (I)'' in which R2 of the general formula (I) obtained by is lower alkoxy, and further converting the hydrolyzate into an acid halide (■),
It can be produced by reacting with a lower alkyl mercaptan, ammonia, a lower alkylamine, or 2,6-ethylaniline.

■ or Engineering ■ )゛ [ ■ ″During the ceremony R1 is mentioned above Same, represents a lower alkoxy group.

] ■ )′ During the ceremony, R1 is the same as above. ) (V) (I)’ (V) In the formula, is the same as above.

] [(1)'' In the formula, P-1 and Rs are the same as above and R6
is the same as above. )] This hydrolysis reaction is usually carried out using an acid or an alkali in an organic solvent, water, or a mixed solvent of water and an organic solvent. Examples of solvents that can be used include alcohols, ethers, and water. Examples of acids that can be used include mineral acids such as hydrochloric acid and sulfuric acid, and examples of alkalis that can be used include sodium hydroxide and potassium hydroxide.

As a treatment method, when hydrolysis is performed using an acid, an organic solvent such as benzene, toluene, or chloroform is added after the reaction, the target product is separated by washing with water as appropriate, and the solvent is distilled off. In addition, in the case of hydrolysis using an alkali, after the reaction is completed, add an acid such as hydrochloric acid to make it acidic, add an organic solvent such as benzene, toluene, or chloroform, wash with water as appropriate, and separate the target product. The solvent is distilled off. The above acid chloride reaction can be carried out by reacting a carboxyl salt conductor of compound (I)' obtained by a hydrolysis reaction with thionyl chloride. Solvents that can be used for this reaction include benzene,
These include hydrocarbons such as toluene and halogenated hydrocarbons such as chloroform. - The amidation reaction or thioesterification reaction between the acid halide of formula (V) and amines or thiols is usually carried out in an organic solvent using an acid binder. Examples of solvents that can be used include hydrocarbons such as benzene and toluene, and halogenated hydrocarbons such as chloroform.

Organic bases such as triethylamine and pyridine can be used as acid binders.

Examples of production by method (C) are shown in Examples 5 and 6.

Acetylene carboxylic acid dimethyl ester 7.

A mixture of 8 g of N-nicotinoylphenylchrysine and 150 m of acetic anhydride was stirred at 140°C for 1 hour. After cooling, acetic anhydride was distilled off under reduced pressure, toluene and water were added, and the organic layer was separated. After washing with water, the solvent was distilled off under reduced pressure to obtain 10.0 g of the title compound as a brown oil.
Obtained. When this is purified by silica gel column chromatography, it becomes white crystals with a melting point of 132-135℃.
showed that.

Acetylenedicarboxylic acid dimethyl ester 71g and N
-)-Lifluoroacetylphenylchrysin 12.4
A mixture of 150 ml of acetic anhydride and 150 ml of acetic anhydride was stirred at 140°C for 2 hours. After cooling, acetic anhydride was distilled off under reduced pressure.
Toluene and water were added, and the organic layer was separated. After washing with water, the solvent was distilled off under reduced pressure to obtain the title compound as a brown oil.
2.9g was obtained. When this was purified by silica gel chromatography, it became a colorless oil with n=1°186.

2-(3-pyridyl)-5-phenyl- obtained in Example 1
3,4-dicarboxylic acid dimethyl ester (compound ND2
) and 2.6 g of pencil chloride were dissolved in 100 rnJJ of dimethylformamide, 500 mg of sodium hydride was added, and the mixture was stirred at 80°C for 2 hours. After cooling, toluene and water were added, and the organic layer was separated. After washing with water, the solvent was distilled off under reduced pressure to obtain 8.0 g of the title compound as a pale brown oil. When this was purified by silica gel column chromatography, it became white crystals with a melting point of 104-106°C.

Example 4 1-Methyl-2-(2-thienyl) Method (A)
2-(2--F-enyl)-5-phenyl-3,4-dicarboxylic acid dimethyl ester (compound N
o1O) 6.8g, methyl iodide 3.0g, potassium carbonate 3.0g and dimethyl sulfoxide 100mJJ
The mixture was stirred at 6°0C for 3 hours. After cooling, wood and toluene were added, and the organic layer was separated. After washing with water, the solvent was distilled off under reduced pressure, and the title compound was obtained as a pale brown oil at 6°5.
g was obtained. When this was purified by silica gel column chromatography, it became white crystals with a melting point of 75-78°C.

6.7 g of 2-(3-pyridyl)-5phenyl-virol-3 4-dicarboxylic acid dimethyl ester (compound Nb2) prepared in Example 1, 2.0 g of sodium hydroxide, 50 mM of ethanol, and 50 m of water.
The mixture was stirred at 70'C for 1 hour. After cooling, add 50 m fL of water, lo of chloroform.

Then, the mixture was made acidic with 55 m of 1 normal hydrochloric acid.

The chloroform layer was separated and the solvent was distilled off under reduced pressure to obtain 6.0 g of the title compound as white crystals. When this is recrystallized from a mixed solvent of hexane and acetone, the melting point is 177.
-180'C was shown.

(C)] 2-(3-pyridyl)-5-phenyl-pyrrole-3,5-dicarboxylic acid produced in Example 5 (Compound No. 1)
A mixture of 6.2 g, 8 g of thionyl chloride, a catalytic amount of pyridine, and 100 mM of benzene was stirred at 60 to 70° C. for 1 hour. After cooling, excess thionyl chloride and benzene were distilled off under reduced pressure. This residual liquid and 2,6-ethylaniline
6゜0g, triethylamine 4.1g, chloroform 1
It was added dropwise to the 00mM mixture at 3°C while cooling with ice water. After the addition, the mixture was stirred at room temperature for 1 hour. After this, 100 m of water
1 was added and the chloroform layer was separated. After washing with water, the solvent is distilled off under reduced pressure to obtain the title compound as pale yellow crystals.
11. og obtained.

When this was recrystallized from a mixed solvent of toluene and acetone, it became white crystals with a melting point of 230-234°C.

The herbicide of the present invention described in Section 2 of Formulation Method of Herbicide can be prepared by adding the compound of general formula (I) to emulsions, wettable powders, liquids, floorfuls (sols), etc. ), powder, trifless (DL) powder, granules, fine granules, and tablets. As the carrier used herein, any solid or liquid carrier that is commonly used for agricultural common medicines may be used, and the carrier is not limited to a specific carrier. For example, these carriers include mineral powders (kaolin, bentonite,
Clay, montmorillonite, talc, diatomaceous earth, mica, vermiculite, gypsum, calcium carbonate, apatite, white carbon, slaked lime silica sand, ammonium sulfate, urea, etc.), vegetable powder (soybean flour, wheat flour, wood flour, tobacco flour, starch) ,
Examples include crystalline cellulose), polymer compounds (petroleum resin, polyvinyl chloride, ketone resin, Danzurcum), alumina, silicates, sugar polymers, highly dispersed silicic acid, and waxes. Liquid carriers include water, alcohols (methyl alcohol, ethyl alcohol, n-propyl alcohol, l5O-propyl alcohol, phthanol, ethylene glycol, benzyl alcohol, etc.), aromatic hydrocarbons (toluene, benzene, xylene, ethyl alcohol, etc.). , methylnaphthalene, etc.), halogenated hydrocarbons (chloroform, carbon tetrachloride dichloromethane, chloroethylene, monochlorohensen, trichlorofluoromethane, dichlorofluoromethane, etc.), ethers (ethyl ether, ethylene oxide, dioxane, tetrahydrofuran, etc.) ), ketones (acetone,
Methyl ethyl ketone, cyclohexanone, methyl isomethyl ketone, inholon, etc.), esters (ethyl acetate, methyl acetate, ethylene glycol acetate, amyl acetate, etc.), acid amides (dimethylformamide, dimethylacetamide, etc.), nitriles ( acetonitrile, propionitrile, acrylonitrile, etc.), sulfoxides (dimethyl sulfoxide, etc.), alcohol ethers (ethylene glycol monomethyl ether,
(ethylene glycol monoethyl ether, etc.), aliphatic or alicyclic hydrocarbons (n-hexane, cyclohexane, etc.), industrial gasoline (petroleum ether, solvent naphtha, etc.), petroleum distillates (paraffins, kerosene, etc.) , light oil), etc.

In addition, various surfactants (or emulsifiers) are used for the purposes of emulsification, dispersion, solubilization, wetting, foaming, lubrication, and spreading when preparing emulsions, wettable powders, and flooring agents. Such surfactants include nonionic types (polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene solhitane alkyl esters, etc.) and anionic types (alkylbenzene sulfonates, alkyl sulfosuccinates, alkyl sulfates, etc.). , polyoxyethylene alkyl sulfate,
arylsulfonate), cationic type (alkylamines (laurylamine, stearyltrimethylammonium chloride, argyldimethylpentylammonium chloride), polyoxyethylene alkylamines), amphoteric type [carboxylic acid (hetaine type), sulfuric acid ester salts, etc.], but the present invention is not limited to these examples.

In addition to these, polyvinyl alcohol (PVA)
It is possible to use various adjuvants such as , carboxydimethylcellulose (CMC), gum arabic, polypyridyl acetate 1-seratin, alkinoic acid sorta, and gum tracacanth.

In the present invention, when producing the various preparations described above, the compound of the present invention is contained in a range of 0.001% to 95% (weight %: the same hereinafter), preferably 0.01% to 90%. It can be formulated into a formulation. For example, usually
For powders, DL powders, and fine powders (F), 0.01%~
In the case of 5% single granules, the content ranges from 0.01% to 10%, and in the case of wettable powders, emulsions, and liquids, the content ranges from 1% to 75%.

For example, in the case of a granule, the preparation prepared in this way is
The active ingredient may be sprayed directly on the soil surface, in the soil, or in water in an amount of about 0.3 to 300 g per 10 are. For wettable powders, emulsions and vines,
It may be diluted with water or a suitable solvent and sprayed in an amount of about 0.3 to 300 g of active ingredient per 10 ares.

Furthermore, when using the compound of the present invention as a herbicide, it may be possible to expand its applicability by mixing it with known herbicides, insecticides, or plant regulators, and in some cases, it may be possible to expect a synergistic effect. Ru.

A method for formulating the compound of the present invention of general formula (I) as a herbicide will be explained with reference to Examples 7 to 1O below. However, the present invention is not limited to these examples, and may be mixed with various other additives in any proportion, and other herbicides as described above may be mixed in any proportion. It can also be made into a formulation.

In addition, the compound defects are shown in Table 1 above,
Furthermore, all parts in the examples refer to parts by weight.

Example 7 (granules) 1 part of compound Th of compound Nol, lauryl sulfate
1 part of calcium ricnin sulfonate, 30 parts of bentonite, and 67 parts of white clay were mixed with 15 parts of water, mixed in a mixer, granulated in a granulator, and dried in a fluidized dryer to obtain the active ingredient. Granules containing 1% are obtained.

Example 8 (Irrigation agent) Compound No. 2 compound 15 parts, white carphone 1
5 parts of calcium likunin sulfonate, 3 parts of polyoxyethylene nonyl phenyl ether, 5 parts of diatom and 60 parts of clay are uniformly mixed in a grinding mixer to obtain a wettable powder containing 15% of the active ingredient. .

Example 9 (emulsion) 20 parts of compound No. 19, Tsurupol 700H
(Emulsifier manufactured by Toho Chemical Industry Co., Ltd.) 20 parts and xylene 60 parts are mixed to obtain an emulsion containing 20% of the active ingredient.

Example 10 (powder) Compound Nb26 0.5 part, silicic anhydride fine powder
0.5 parts of calcium stearate, 0.5 parts of calcium stearate, 50 parts of clay and 48.5 parts of talc are uniformly mixed and ground to obtain a powder containing 0.5% of the active ingredient.

Effects of the Invention The compound of the present invention represented by general formula (I) has superior herbicidal activity and safety compared to known similar compounds.

That is, the compound of the present invention acts extensively on paddy field weeds such as barnyard grass, firefly, grasshopper, konaki, azalea, and kikashikusa. Many weeds can be almost completely eradicated by treatment. In addition, it is possible to almost completely eliminate various upland weeds such as crabgrass, foxtail grass, whiteweed, dogweed, and knotweed by applying 100 g of the active ingredient per 10 are. Moreover, it does not cause any chemical damage to useful crops such as paddy rice, corn, corn, heat, rapeseed, and wheat.

Furthermore, it is not toxic to humans or fish. It's safe to use if you want.

- Test Examples 1 and 2 are shown to illustrate the herbicidal activity of the compound of the present invention represented by formula (I).

A Wachner pot with a size of 175,000 are is filled with paddy soil (alluvial loam), and the surface layer is filled with barnyard grass, firefly,
Fifty seeds each of Helaomotaka, Konaki, Asena, and Kikashigusa were uniformly sown. Flooded one day after sowing,
The water depth was kept at 2 cm. Three days after sowing, two 2.5-leaf stage seedlings of paddy rice were planted, and three plants were transplanted per pot. One day after transplanting paddy rice, an emulsion prepared according to Example 9 was diluted with water, and 10mjL per pot (equivalent to 50 g per 1OmjL in terms of the amount of active ingredient used) was added dropwise.

This test was conducted in duplicate per 1 drug solution concentration section, and the drug treatment
After a day, the herbicidal effect and the degree of phytotoxicity of paddy rice were investigated based on the evaluation index shown below.

The results are shown in Table 2.

Weeding rate (%) 100% Less than 80-1OO% 60-801, 40-60I1 20-401, 20Nl Evaluation value of drug damage Degree of drug damage Blight Plant damage Major I Medium Small horn Slight Is Table (UK) Compound e5 described in Patent No. 2194788
>(-Film formation/Futachlor) Test Example 2 Herbicidal effect on field weeds and crops 1) Test of herbicidal effect on weeds Field soil (
Alluvial loam) was packed, and 50 seeds each of various weeds such as crabgrass, foxtail grass, whiteweed, Japanese knotweed, and Japanese knotweed were evenly mixed with the soil in the surface layer of 1 cm, and one surface layer was lightly pressed.

Two days after sowing, the emulsion prepared according to Example 9 was diluted with water, and 1001 treatment chemicals per 10 are (equivalent to 100 g per 10 are in terms of application amount of active ingredient) were sprayed onto the soil surface. did.

This test was conducted in duplicate per 1 drug solution concentration section, and the drug treatment
Days later, the herbicidal effect was investigated based on the same evaluation index as in Test Example 1.

2) Test for phytotoxicity on crops Fill field soil (alluvial loam) in 1/10,000 are clay pots, and add seeds of each crop (5 dice, 5 corn, 10 beets, 10 rapeseed, and 10 wheat).
The grains were sown in separate pots, and the surface layer was lightly pressed. One day after sowing, an emulsion prepared according to Example 9 was diluted with water, and a treatment agent of 100 per 10 are (active ingredient amount equivalent to 100 g per 10 are) was sprayed onto the soil surface.

This test was conducted in duplicate per 1 drug solution concentration section, and the drug treatment
Days later, the degree of chemical damage to each crop was investigated based on the same evaluation index as in Test Example 1. The results are shown in Table 3.

Claims (1)

[Claims] 1) General formula ▲ Numerical formula, chemical formula, table, etc. Alkylthio group, ▲mathematical formula, chemical formula,
There are tables, etc. ▼ (In the formula, R_4 and R_5 may be the same or different hydrogen atoms, lower alkyl groups, 2,6-
Indicates diethylphenyl group. ), and R_3 represents a pyridyl group, thienyl group, furyl group, or trifluoromethyl group. ) A pyrrole dicarboxylic acid derivative represented by 2) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R_1 represents a hydrogen atom, lower alkyl group, phenyl lower alkyl group, R_2 represents a hydroxyl group, lower alkoxy group, lower alkylthio group, ▲ Numerical formula, Chemical formula,
There are tables, etc. ▼ (In the formula, R_4 and R_5 may be the same or different hydrogen atoms, lower alkyl groups, 2,6-
Indicates diethylphenyl group. ), and R_3 represents a pyridyl group, thienyl group, furyl group, or trifluoromethyl group. ] A herbicide characterized by containing a pyrrole dicarboxylic acid derivative represented by the following as an active ingredient.