JPH04117357A - 4-ethyl-3-(substituted phenyl)-1-(3-substituted phenyl) pyrrolidine-2-one derivative and herbicide with the same as active ingredient - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (X is alkyl, alkoxy, phenoxy, cyano, nitro, OH, H or halogen; Y is H, halogen or alkyl; Z is H, halogen or CF3; n is 1, 2 or the number of substituents expressed by Z). EXAMPLE:4-Ethyl-3-(3-fluorophenyl)-1-(3-methylphenyl)pyrrolidine-2-one. USE:A herbicide highly effective even at low dosage also causing no chemical injury. PREPARATION:The objective compound can be obtained by reductively cyclization of an amide derivative of formula II (W is halogen). Said amide derivative of the formula II can be prepared by reaction between an amine of formula III and a carboxylic acid derivative of formula IV (Q is halogen).

Description

[Detailed description of the invention] Industrial field of application] The present invention provides novel 4-ethyl-3-(substituted phenyl)-1
(3-substituted phenyl) pyrrolidin-2-one derivative,
and herbicides containing these compounds as active ingredients.

[Prior Art] It has already been disclosed that certain 2-pyrrolidinone derivatives have herbicidal activity;
It is described in, for example, Japanese Patent No. 0-58960. Further, US Pat. No. 4,132.713 discloses a method for producing 2-pyrrolidinone derivatives.

JP-A-52-89666 and 58-154558
The representative compound 3-chloro-4- disclosed in the publication No.
(chloromethyl) -1-(3-)lifluoromethylphenyl)-2-pyrrolidinone (-ship name, fluoroc
chloridone) is commercially available.

[The invention tries to solve the problem 1! I! 11 The above-mentioned Japanese Patent Publication No. 5
The compounds disclosed in No. 2-89666 and the compounds disclosed in JP-A-58-154558 require relatively large doses when used as herbicides. When used in paddy fields, there is a problem in that even though the dosage is effective against some noxious weeds, it causes severe damage to rice, which is a useful crop.

Therefore, the present invention does not harm useful crops in paddy fields and field crops, and is effective against harmful weeds at low doses.
The objective is to provide selective weeding.

[Means and effects for solving the problem] The present inventors have developed a herbicide that is more effective at a lower dosage than conventional herbicides,
In order to obtain a herbicide with no chemical damage, we conducted further research on 2-pyrrolidinone derivatives, and found that they have specific phenyl groups at the 1- and 3-positions of the pyrrolidinone ring, and an ethyl group at the 4-position. A novel 4-ethyl-3-
It has been found that (substituted phenyl)-1-(3-1F substituted phenyl)pyrrolidin-2-one derivatives are extremely effective as herbicides and have the characteristic of not causing any phytotoxicity to useful crops.

4-ethyl-3-(substituted phenyl)-1-(3
The -substituted phenyl)pyrrolidin-2-one derivative is characterized by being represented by the following -Funezo (1).

(In the formula, X represents a lower alkyl group, lower alkoxy group, phenoxy group, cyano group, nitro group, hydroxyl group, hydrogen atom, or halogen atom, Y represents a hydrogen atom, halogen atom, or lower alkyl group, and Z represents hydrogen atoms, halogen atoms,
It represents a trifluoromethyl group, n is 1 or 2 and represents the number of substituents represented by Z, and Z when n=2 may be the same or different. ) Furthermore, the herbicide of the present invention contains a 4-ethyl-3-(substituted phenyl)-1-(3-substituted phenyl)pyrrolidin-2-one derivative represented by the above-mentioned -Funakura (I) as an active ingredient. The compounds disclosed in JP-A-52-89666 and JP-A-58-154558 require relatively large doses when used in actual fields, particularly in paddy fields. Because it causes serious toxicity to rice, its use is extremely limited.

In contrast, the compound of the present invention not only can be applied to upland crops at a lower dose, but also has high safety against rice in paddy fields, so its range of application has been greatly expanded.

The compound according to the present invention has a structure equal to or less than that of the prior art compound! The halogen atom at the 3-position of the pyrrolidinone ring is converted to a specific phenyl group, the chloromethyl group at the 4-position is converted to an ethyl group, and the m-trifluoromethyl group at the 1-position is converted to a specific phenyl group. It differs in that it is This conversion achieved high activity as a herbicide and expanded the range of selectivity between rice and weeds in rice fields, making it easier to use in rice fields.

The herbicide containing the compound of the present invention as an active ingredient is effective against harmful weeds that are a problem in most paddy fields or fields, such as grass weeds such as paddy field weeds, cyperus japonica, and firefly. It has an excellent herbicidal effect on perennial broad-leaved weeds such as Cyperaceae weeds and Japanese cucumber, and in fields, against broad-leaved weeds such as cyperus, hotokenoza, and chickweed, and grass weeds such as crabgrass and oat. On the other hand, rice and wheat, which are useful crops,
The herbicides related to the compounds of the present invention, which do not cause any phytotoxicity to corn, dice, cotton, etc., are effective in all treatment methods such as water-transfer soil treatment, soil treatment, soil mixed layer treatment, and foliar spray treatment.

4-ethyl-3-(substituted phenyl)-1-(3
The -f-substituted phenyl)pyrrolidin-2-one derivative is a new compound and can be produced by the method described below.

That is, it can be easily produced by subjecting an amide derivative represented by the -11ffi formula (It) to a reductive cyclization reaction.

(In the above reaction formula, X, Y, Z, and n have the same meanings as above, and W represents a halogen atom.) A cyclizing agent effective for this cyclization reaction is represented by tributyltin hydride. Examples include trialkyltin hydride, and in boat fishing, the reaction is carried out in an aromatic solvent such as benzene, toluene, or xylene. The reaction temperature is preferably 50 to 140°C, more preferably 60 to 90°C, and a catalytic amount of α, α-
The reaction proceeds by adding a radical generator, such as abbisisobutyronitrile or benzoyl peroxide, to the reaction mixture. Irradiation with light is also an effective means.

The amide derivative represented by general formula (II) is
It can be produced by reacting the amine of [) with the carboxylic acid derivative of general formula (TV).

(III) (In the above formula, X, Y, Z, W, n have the same meanings as above,
Q represents halogen. ) The reaction is carried out without a solvent or in an inert solvent, and inert solvents include aromatics such as benzene, toluene, xylene, chlorobenzene, and dichlorobenzene, and halogenated hydrocarbons such as dichloromethane, chloroform, and carbon tetrachloride. Examples include ethers such as diethyl ether, tetrahydrofuran, and dioxane, and esters such as ethyl acetate and butyl acetate. In addition, aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide are also effective. The reaction proceeds at any temperature, and triethylamine, pyridine, N.

The reaction may be carried out in the presence of a base such as N-dimethylaniline, sodium hydride, potassium hydride, sodium carbonate, potassium carbonate, or sodium hydrogen carbonate.

Amines of formula (Ill) are described in U.S. Pat.
Manufactured by the method described in, etc. Also, the general formula (
The acid halide (ii) can be produced from a manzolin acid derivative or a phenylacetic acid derivative by a known method.

Furthermore, the 4-ethyl-3-(substituted phenyl)-1-(3-If substituted phenyl)pyrrolidin-2-one derivative according to the present invention can be used to reduce the 2-pyrrolidinone derivative represented by the general formula (V). It can also be produced by dehalogenation.

(In the above reaction formula, X, Y, Z, W, and n have the same meanings as above.) This reaction is carried out without a solvent or in a solvent in the presence of a suitable reducing agent. Examples of reducing agents include metals such as iron, zinc, tin, and copper, dialkyltin hydrides such as dibutyltin hydride, trialkyltin hydrides such as tributyltin hydride, diphenyltin hydride, and triphenyltin hydride. Examples include organic tin compounds. It is also possible to carry out the reaction using hydrogen in the presence of palladium carbon, tofu-nickel, platinum, etc. Depending on the case, methods such as electrolytic reduction are also effective. Suitable solvents include aromatics such as benzene, toluene and xylene, ethers such as dioxane, tetrahydrofuran and diethyl ether, esters such as ethyl acetate and butyl acetate,
Examples include lower alcohols such as methanol, ethanol, propatool, and butanol, and lower organic acids such as acetic acid, propionic acid, and butyric acid.The reaction temperature is 0 to 16.
0°C, and the reaction time may be from several seconds to 50 hours, and the reaction may be carried out at the reflux temperature of the solvent. It is also possible to carry out the reaction in the presence of acids.

The 2-pyrrolidinone derivative represented by general formula (V) is
It is produced by subjecting the amide derivative of general formula (n) to a cyclization reaction in the presence of a suitable catalyst.

(II) (In the above reaction formula, X, Y, Z, W, and n have the same meanings as above.) The reaction is generally carried out in a solvent, and preferred solvents are those that do not interfere with the reaction, i.e. , diethylene glycol dimethyl ether, dimethyl formamide, dimethyl acetamide, dimethyl sulfoxide, acetonitrile, benzene, toluene, xylene, etc. Suitable catalysts are preferably transition metal catalysts, such as ferrous ions or cuprous ions. Specific transition metal catalysts include ferrous chloride and cuprous chloride. It is also very effective to add amines to the reaction mixture in order to accelerate the reaction.The reaction temperature is 20 to 190°C, preferably 70 to 140°C.
It is.

The compound represented by the general formula (1) according to the present invention obtained in this way is generally mixed with an inert liquid carrier or a solid, and prepared in the commonly used formulation forms of powders, granules,
It is adjusted and used in wettable powders, emulsions, flowables, etc.

Furthermore, if necessary for cleaving, an auxiliary agent can be added.

As the carrier, any solid or liquid carrier commonly used in agricultural and horticultural chemicals can be used, and the carrier is not limited to a specific one. For example, solid carriers include mineral powders such as clay, talc, bentonite, calcium carbonate, diatomaceous earth, and white carbon;
Examples include vegetable powders such as soybean flour and starch, polymeric compounds such as petroleum resins, polyvinyl alcohol, and polyalkylene glycols, urea, and waxes.

Examples of the liquid carrier include various organic solvents such as xylene, toluene, methylnaphthalene, and alkylbenzene, and water.

As adjuvants, surfactants, binders, stabilizers, etc. commonly used in agricultural and horticultural chemicals can be used singly or in combination as required. Further, depending on the case, an industrial sterilizer or an antibacterial agent may be added for antibacterial and antifungal properties.

As examples of surfactants, nonionic, anionic, cationic, and amphoteric surfactants can be used individually or in combination as appropriate. As non-ionic materials, preferred are alkylphenols, higher alcohols, alkylnaphthols, higher fatty acids, fatty acid esters, etc. to which ethylene oxide or propylene oxide is added.As anionic materials, alkylphenols, alkylnaphthols, Preferred are alkyl sulfonates, alkyl sulfate ester salts, phosphate ester salts, etc. of higher alcohols, higher fatty acids, fatty acid esters, etc., and lignin sulfonate salts are also preferred.

The content of the compound represented by general formula (1) in the herbicide according to the present invention varies depending on the formulation, but is usually 0.01 to 20% by weight for powders, 1 to 50% by weight for wettable powders, and 1 to 50% by weight for granules. 0.01-141% for emulsion, 1-50% for emulsion
% by weight, 1 to 50% by weight for flowable formulations, and 1 to 50% by weight for dry flowable formulations, preferably,
0.1-3% by weight for powders, 10-40% by weight for wettable powders, 0.1-5% by weight for granules, 10-30% by weight for emulsions, 20-30% by weight for flowable preparations, dry flowables In formulations it is 20-40% by weight.

The herbicide according to the present invention includes other herbicides or fungicides,
It can be used in combination with insecticides, plant growth regulators, fertilizers, soil conditioners, etc., and synergistic effects can be expected in some cases.

[Example] The method for synthesizing the compound of the present invention will be explained by giving examples.

Example 1 4-ethyl-3-(3-fluorophenyl)-1-(3
Synthesis of -methylphenyl)pyrrolidin-2-one (compound number 1.2) In 30 d of toluene, N-(2-butenyl)-N-(3-
Add 3.8 g of methylphenyl)-2-bromo-2-(3-fluorophenyl)acetamide, and while stirring at 80-90°C, add 3.6 ad of tributyltin hydride and α,α-abbisisobutyro A very small amount of nitrile (AIBN) was added and stirring was continued for 1 hour. Next, toluene was distilled off using an evaporator, and the remaining liquid was dissolved in acetonitrile 100. After thorough washing with rhohexane, the solvent was distilled off using an evaporator to obtain 3.3 g of an oily substance. By performing silica gel chromatography on this oil, 3
．． 4-trans isomer 1.23g, and 34-cis isomer 0
．． 44g was obtained.

Example 2 3.4-) Synthesis of lance-4-ethyl-3-(3-fluorophenyl)4-(3-hydroxyphenyl)pyrrolidin-2one (Compound No. 14) 3.4-) lance-4- Ethyl-3-(3-fluorophenyl)4-(3-methoxyphenyl)pyrrolidine-
2-one (compound number 13; synthesized according to Example 1)
8.3 g was heated at reflux temperature for 2 hours with stirring with 47% hydrogen bromide. The mixture was cooled to room temperature, extracted with 100 m of diethyl ether, and washed with saturated brine. Next, after drying with sodium sulfate, the ether was distilled off,
By performing silica gel column chromatography, 6.8 g of the target compound was obtained.

According to the methods of Examples 1 and 2, other 4-ethyl-3-(1j
(substituted phenyl)-1-(3-substituted phenyl)pyrrolidine-
A 2-one derivative was synthesized.

Table 1 shows the thus obtained compounds represented by the general formula (1) according to the present invention and their physical properties.

Further, examples of synthesis of important intermediates for synthesizing the compound of general formula (1) of the present invention are shown below as reference examples.

Reference Example I N-(2-butenyl)-N-(3-methylphenyl)-
Synthesis of 2-furomo 2-(3-fluorophenyl)acetamide 3.2 g of N-(2-butenyl)-1 toluidine,
Melt 2.5d of pyridine in 40d of methylene chloride,
6.0 g of bromo-2-(3-fluorophenyl)acetyl chloride was gradually added dropwise at 20 to 30°C with stirring. After stirring for an additional 15 minutes, methylene chloride was distilled off, and the residue was then poured into 10% aqueous hydrochloric acid and extracted with toluene. The toluene solution was washed with saturated aqueous sodium bicarbonate and saturated brine, dried over anhydrous sodium sulfate, and then the toluene was distilled off using an evaporator to quantitatively obtain the desired product.

Reference Example 2 Synthesis of N-(2-butenyl)-w-toluidine In dimethylformamide 40 paper, to 5.4 g of totoluidine, 6.9 g of anhydrous potassium carbonate and 7.3 g of 1-chloro-2-butene
d was added and stirred at 75°C to 85°C for 3 hours. After filtering off potassium carbonate, it was poured into 200ml of saturated brine, extracted with toluene, the toluene was distilled off, and silica gel column chromatography was performed to obtain the desired compound 6. Obtained Og.

(Sheet weight 74%) Reference Example 3 Synthesis of 2-bromo-2-(3-fluorophenyl)acetyl chloride 14 g of thionyl chloride was added to 15.4 g of 3-fluorophenyl acetic acid, and while stirring and heating to reflux, bromine was added. 18g
After the completion of the dropwise addition, heating and refluxing was continued for 30 hours, and after cooling, the mixture was concentrated using an evaporator to quantitatively obtain the target acid chloride.

[Formulation Examples and Test Examples] Next, formulation examples and herbicidal activity test examples of the herbicide according to the present invention will be shown.

Formulation example 1 (hydrating powder) Compound of the present invention (1): 20 parts by weight, Neoperex (trade name, manufactured by Kao; sodium dodecylbenzenesulfonate) = 2 parts by weight, Neugen EA (trade name, manufactured by Dai-Kogyo Seiyaku) ; polyoxyethylene nonylphenyl ether) :2
Parts by weight, 85 parts by weight of white carbs and ±71 parts by weight of diatoms
Parts by weight were thoroughly ground and mixed to obtain a wettable powder.

Formulation Example 2 (Powder) Compound of the present invention (3): 1 part by weight, Emulgen 910 (trade name, manufactured by Kao; polyoxyethylene nonylphenyl ether): 0.5 part by weight, and kaolin clay: 98.
5 parts by weight were thoroughly ground and mixed to obtain a powder.

Formulation Example 3 (Granules) 1 part by weight of the finely ground compound of the present invention (5), Neoperex (trade name, same as above); 2 parts by weight, Sunextract P2
52 (trade name, manufactured by Sanyo Kokusaku Valve; sodium lignin sulfonate) = 2 parts by weight, bentonite: 72 parts by weight, and talc - 23 parts by weight were thoroughly mixed, then an appropriate amount of water was added to moisten the mixture, and then a small It was extruded and granulated using an injection molding machine. This was air-dried at 30 to 60°C and crushed, and then granulated to a size of 0.3 to 2-- using a granulator to obtain granules.

Formulation Example 4 (Breast autopsy) Compound of the present invention (7): 10 parts by weight, Tsurpol 800
A (trade name, manufactured by Toho Chemical: mixture of nonionic surfactant and anionic surfactant): 10 parts by weight and Q-
Xylene: 80 parts by weight were mixed and melted to obtain the back side.

Formulation Example 5 (Flowable agent) 30 parts by weight of the compound of the present invention (11) and 10 parts by weight of Sunextract P252 (trade name, same as above) dissolved in 50 parts by weight of water were wet-pulverized and mixed, and the condensate was mixed. 9.6
Add and mix 0.2 parts by weight of Kelsan S (trade name, manufactured by Kelco; xanthan gum) and 0.2 parts by weight of Pulltop (trade name, manufactured by Takeda Pharmaceutical Industries, Ltd.; organic iodine-based fungicide) dissolved in parts by weight. and obtained a flowable agent.

Test Example 1 Flooded soil treatment test (pre-emergence treatment) 11500
Soil was packed in a 0.00 Earl Wagnerbottle, and seeds or tubers of Japanese cabbage, firefly, urikawa, cypress, and cypress were sown and the water was kept in a warm water condition. Two paddy rice seedlings (2-3 leaf stage) that had been raised in advance were used as one plant, and the two plants were transplanted and grown in a greenhouse. One day later (before weed emergence), a predetermined amount of the test compound was treated using granules prepared according to the method described in Formulation Example 3 above, and after 30 days, the growth status of weeds and chemical damage to paddy rice were evaluated. The situation was observed and investigated. The results are shown in Table 2.

In the table, the degree of damage to the test plants and the degree of phytotoxicity to paddy rice are expressed by comparing the growth state of the plants with those without treatment and using the following criteria.

Growth rate (X) shown in air dry weight ratio vs. untreated area 0-5
(Death 6-10 (Quality book 11-40 (Nakayoshi 41-70) Small book 71-90 (Slightly harmful 91-100 (Harmless) Comparative compounds A and B represent the following compounds,
(Similar to Test Examples 2 and 3) A: 1-(3-trifluoromethylphenyl)-3-oo-4-chloromethyl-2-pyrrolidinone B: l-methyl-3-phenyl-5-(3-) (Lifluoromethylphenyl)-pyridin-4(111)-one In this test, the herbicidal agent according to the present invention showed a higher herbicidal effect on the tested paddy weeds compared to comparative drugs A and B. , and showed excellent safety against paddy rice.

Test Example 2 Upland soil treatment test (pre-emergence treatment) 1 /25
Fill 00 are resinous pots with upland soil, sow corn, wheat, and soybeans, and mix the seeds of barnyard grass, foxtail grass, chickweed, shepherd's purse, morning glory, and rice grass with soil of 2 to 3 c- The plants were covered with soil and grown in a greenhouse. One day later (before the emergence of weeds), a predetermined amount of the test compound was diluted with water using a wettable powder prepared according to the method described in Formulation Example 1 above, and a sprayed liquid volume equivalent to 101 per are was prepared. Then, the soil surface was evenly distributed using a pressurized micro-frost fence. After 30 days, the growth status of weeds and the status of chemical damage to the crops were observed and investigated. The results are shown in Table 3. In the table, the degree of damage to the test plants and the degree of phytotoxicity to crops are shown in the same manner as in Test Example 1.

In this test, the compound according to the present invention was compared with comparative drug A
, B showed a high herbicidal effect on the field weeds tested, and showed excellent safety against the crops corn, wheat, and soybean.

Test Example 3 Field Soil Treatment Test 1 A /10,000 are resin pot was filled with field soil, and each type of morning glory, Japanese knotweed, chickweed, white grass, barnyard grass, crabgrass, corn, and wheat were sown one by one and grown in a greenhouse. Ta. When each plant has 2 to 3 leaves, a predetermined amount of the test compound is diluted with water in an emulsion prepared according to the method described in Dehiscence Example 4 above, and a spray liquid equivalent to 51 per are is prepared. The amount was evenly distributed using a pressurized microspreader. After 30 days had elapsed after the chemical spraying, we conducted an observational investigation of the growth status of weeds and the status of chemical damage to crops.The results are shown in Table 4.In Table 1, the degree of damage to the test plants;
and the degree of phytotoxicity to crops were displayed in the same manner as in Test Example 1.

In this test, the compound according to the present invention was compared with comparative drug A
, B showed a high herbicidal effect on the field weeds tested, and showed excellent safety against corn and wheat crops.

〔Effect of the invention〕

4-ethyl- represented by general formula (I) according to the present invention
The 3-(substituted phenyl)-1-(3-2 substituted phenyl) pyrrolidin-2-one derivative is a new compound, and herbicides containing the compound of the present invention can be used to kill various weeds that are problematic in rice fields and fields. It exhibits remarkable herbicidal activity at extremely low doses, and has a wide herbicidal spectrum. On the other hand, for various useful crops, especially rice in paddy fields,
It shows excellent selectivity and can be used extremely safely.

Claims (2)

[Claims] (1) General formula (I) ▲Mathematical formula, chemical formula, table, etc.▼(I) (In the formula, X is a lower alkyl group, lower alkoxy group, phenoxy group, cyano group, nitro group, hydroxyl group, hydrogen atom, halogen represents an atom, Y represents a hydrogen atom, a halogen atom, or a lower alkyl group; Z represents a hydrogen atom, a halogen atom,
It represents a trifluoromethyl group, n is 1 or 2 and represents the number of substituents represented by Z, and Z when n=2 may be the same or different. ) 4-ethyl-3-(substituted phenyl)-1-
(3-substituted phenyl)pyrrolidin-2-one derivative. (2) General formula (I) ▲Mathematical formula, chemical formula, table, etc.▼(I) (In the formula, X is a lower alkyl group, lower alkoxy group, phenoxy group, cyano group, nitro group, hydroxyl group, hydrogen atom, halogen represents an atom, Y represents a hydrogen atom, a halogen atom, or a lower alkyl group; Z represents a hydrogen atom, a halogen atom,
It represents a trifluoromethyl group, n is 1 or 2 and represents the number of substituents represented by Z, and Z when n=2 may be the same or different. ) 4-ethyl-3-(substituted phenyl)-1-
A herbicide characterized by containing a (3-substituted phenyl)pyrrolidin-2-one derivative as an active ingredient.