JPH0525127A - 3,4-trans-4-ethyl-3-(substituted phenyl)-1-(3-isopropylphenyl)-2-pyrrolidinone derivative and herbicide comprising the same derivative as active ingredient - Google Patents

Abstract

PURPOSE:To obtain a new pyrrolidinone derivative useful as a selective herbicide for paddy fields, not providing rice plant with phyrototoxicity, effectively usable in a wide period before emergence to a growing period after emergence. CONSTITUTION:A 3,4-trans-4-ethyl-3-(substituted phenyl)-3-(3-propylphenyl)-2- pyrrolidinone derivative shown by formula I (X is F, Cl or Br replaced at the 3-position of F replaced at the 3- and 4-positions or at the 3- and 5-positions) such as 3,4-trans-4-ethyl-3-(3-fluorophenyl)-1-(3-isopropylphenyl)-2-pyrrolidi one. The compound is obtained by reducibly dehalogenating a compound shown by formula III. The compound shown by formula I or the compound shown by formula III is readily produced by subjecting a compound shown by formula IV (Y is halogen; R<2> is H or halogen except for F) to ring formation.

Description

Detailed Description of the Invention

[0001]

The present invention relates to novel 3,4-trans-4-ethyl-3- (substituted phenyl) -1- (3-isopropylphenyl) -2-pyrrolidinone derivatives and herbicides containing these as active ingredients. Regarding agents.

[0002]

2. Description of the Related Art It has already been disclosed that certain 2-pyrrolidinone derivatives have herbicidal activity.
89666, JP-A-60-58960, US Pat. No. 4,874,422, EP387,869 and the like. In addition, 3-chloro-4-chloromethyl-1- (3-trifluoromethylphenyl) -2-pyrrolidinone (generic name, fluorochloridone;
One) is commercially available. Also, US Pat.
No. 0,457 discloses a pyrrolidinone derivative represented by the general formula (Formula II) (Chemical Formula 3) and a herbicide.

[0003]

[Chemical 3]

(In the formula, m represents 1, 2, 3, 4 or 5 and n represents 0, 1, 2, 3, 4 or 5. R ¹ is a halogen atom, a trifluoromethyl group or a cyano group. , An alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and may be the same or a combination when m is larger than 1. R ² is selected from a hydrogen atom or a halogen atom. R ³ is selected from a halogen atom, a trifluoromethyl group, a cyano group, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms, and when n is greater than 1, they are the same. And R ⁴ is selected from an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms substituted with halogen.)

[0005]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
The compounds disclosed in Japanese Patent No. 666, JP-A-60-58960 and U.S. Pat. No. 4,874,422 require a relatively large dose when used as a herbicide,
In particular, when these compounds are used in paddy fields, there is a problem of causing serious phytotoxicity to rice, which is a useful crop.

The compounds disclosed in Examples of EP387,869 or US Pat. No. 4,960,457 are
When used in paddy fields, there is a problem that the effect on weeds in the growing season after emergence is low.

Therefore, the present invention provides a selective herbicide which does not harm rice in a paddy field, has a low dose, and can be used over a wide period from pre-emergence to post-emergence growth. Is an issue.

[0008]

Means and Actions for Solving the Problems As a result of further research on the 2-pyrrolidinone derivative to solve the above problems, the present inventors have found that the pyrrolidinone ring has a specific phenyl group at the 1-position and the 3-position. And a novel 3,4-trans-4-ethyl-3- (substituted phenyl) -1- (3-isopropylphenyl) -2 having an ethyl group at the 4-position
It has been found that the pyrrolidinone derivative is extremely excellent as a herbicide and has a characteristic that it does not cause phytotoxicity to rice, which is a useful crop.

3,4-trans-4-ethyl-of the present invention
The 3- (substituted phenyl) -1- (3-isopropylphenyl) -2-pyrrolidinone derivative is characterized by being represented by the general formula (I) (Formula 4).

[0010]

[Chemical 4] (In the formula, X represents a fluorine atom substituted at the 3-position, a chlorine atom, a bromine atom, a fluorine atom substituted at the 3-position and the 4-position, or a 3-position and the 5-position)

Japanese Unexamined Patent Publication Nos. 52-89666 and 6
The compounds disclosed in 0-58960 and U.S. Pat. No. 4,874,422 cannot be used because they cause serious chemical damage to rice when used in paddy fields.

In the compound of the present invention, a 3-isopropylphenyl group is introduced into the 1-position of the pyrrolidinone ring, a specific phenyl group is introduced into the 3-position of the pyrrolidinone ring, and an ethyl group is introduced into the 4-position of the pyrrolidinone ring. It is characterized by being a transformer.

On the other hand, US Pat. No. 4,960,457 discloses a compound represented by the general formula (II) (formula 5).

[0014]

[Chemical 5]

(In the formula, m represents 1, 2, 3, 4 or 5 and n represents 0, 1, 2, 3, 4 or 5. R ¹ is a halogen atom, a trifluoromethyl group or a cyano group. , An alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and may be the same or a combination when m is larger than 1. R ² is selected from a hydrogen atom or a halogen atom. R ³ is selected from a halogen atom, a trifluoromethyl group, a cyano group, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms, and when n is greater than 1, they are the same. R ⁴ is selected from an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms substituted with halogen.) That is, US Pat.
0,457 includes the compounds of the present invention in a superordinate concept. However, although U.S. Pat. No. 4,960,457 claims a very broad range of compounds, the example compounds are limited. For example, the examples of R ¹ defined in the above general formula (II) are limited to trifluoromethyl group, cyano group, chlorine atom and fluorine atom, and the examples in which R ¹ is an alkyl group are described. Not not.

The compounds described in the examples of US Pat. No. 4,960,457, or the compounds described in EP387869 are less effective against weeds in the post-emergence growing season when used in paddy fields. Therefore, its usage is limited only before the emergence of weeds.

The compound of the present invention has a 3-isopropylphenyl group at the 1-position of the pyrrolidinone ring, a specific phenyl group at the 3-position of the pyrrolidinone ring, and an ethyl group at the 4-position. The feature is that it is a transformer. The significance of arranging these specific substituents, in particular, the significance of introducing a 3-isopropylphenyl group at the 1-position of the pyrrolidinone ring is great, and by this conversion, high activation as a herbicide was achieved, From the weeds of to the weeds in the growing season after emergence, it shows high herbicidal activity,
Therefore, the paddy field can be applied over a wider period.

The herbicides containing the compound of the present invention as an active ingredient have, as their action characteristics, harmful weeds that are problematic in most paddy fields, for example, grass weeds such as Nobie, Cyperaceae weeds such as Cyperaceae and Firefly, and Cucurbitaceae. It has an excellent herbicidal effect on perennial weeds such as. On the other hand, it is not harmful to rice, which is a useful crop. Further, the herbicide relating to the compound of the present invention can be effectively used in all treatment methods such as flooded soil treatment, soil treatment, and soil admixture treatment, over a wide period of the growth period from before weeds to after weeds.

3,4-trans-4-ethyl-of the present invention
The 3- (substituted phenyl) -1- (3-isopropylphenyl) -2-pyrrolidinone derivative is a novel compound and can be produced by the method represented by the reaction formula (I).

[0020]

[Chemical 6]

That is, in the general formula (III) (wherein, X is a fluorine atom substituted at the 3-position, a fluorine atom substituted at the 3-position and the 4-position or a fluorine atom substituted at the 3-position and the 5-position is represented by R Is a halogen atom other than a fluorine atom.) And is produced by reductively dehalogenating a pyrrolidinone derivative.

This reaction can be carried out in the presence of a catalyst such as palladium carbon or Raney nickel in a suitable solvent, with or without hydrogen. Suitable solvents include, for example, aromatics such as benzene, toluene and xylene, ethers such as dioxane, tetrahydrofuran and diethyl ether, esters such as ethyl acetate and butyl acetate, lower alcohols such as methanol, ethanol, propanol and butanol. And lower organic acids such as acetic acid, propionic acid and butyric acid, and aprotic solvents such as dimethylformamide. The reaction temperature is 0 to 160
The reaction may be carried out at the reflux temperature of the solvent. Also,
It is also possible to carry out the reaction in the presence of acetic acid, formic acid, an alkali metal salt thereof, sodium hypophosphite or the like.

The pyrrolidinone derivative represented by the general formula (I) or the general formula (III) of the compound of the present invention is
It is produced by the method represented by the reaction formula (II).

[0024]

[Chemical 7]

That is, the general formula (IV) (in the formula, X is 3
A fluorine atom, a chlorine atom, a bromine atom, which is substituted in the -position, 3
Fluorine atoms substituted at the -position and 4-position, or at the 3-position and 5-position, Y is a halogen atom, R ² is a hydrogen atom, or a halogen atom other than a fluorine atom. It can be easily produced by subjecting the amide derivative represented by the formula 4) to a cyclization reaction. Examples of the cyclizing agent effective for this cyclization reaction include trialkyltin hydride represented by tributyltin hydride, and the reaction is generally carried out in an aromatic solvent such as benzene, toluene and xylene. . The reaction temperature is 50 to 140 ° C., preferably 80 to 1
It is 20 ° C. The reaction proceeds by adding a radical generator such as a catalytic amount of α, α-azobisisobutyronitrile or benzoyl peroxide to the reaction solution. Irradiating with light is also an effective means. Further, after the completion of the reaction, a method of treating with a suitable alkali is also effective in order to obtain the desired 3,4-trans isomer in good yield.

The amide derivative represented by the general formula (IV) is produced by the method represented by the reaction formula (III) (chemical formula 8).

[0027]

[Chemical 8]

That is, the amine of the general formula (V) (wherein R ² has the same meaning as described above) and the amine of the general formula (VI) (wherein, X and Y have the same meanings as described above, and Z is It can be produced by reacting a carboxylic acid derivative having a halogen atom. The reaction is carried out without solvent or in an inert solvent, and examples of the solvent include aromatics such as benzene, toluene, xylene, chlorobenzene and dichlorobenzene, ethers such as dioxane, tetrahydrofuran and diethyl ether, ethyl acetate and butyl acetate. And the like, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride and the like.
Further, aprotic solvents such as dimethylformamide and dimethylsulfoxide are also effective. The reaction proceeds at any temperature, and triethylamine, pyridine, N, N
-The reaction may be carried out in the presence of a base such as dimethylaniline, sodium hydride, potassium hydride, sodium carbonate, potassium carbonate, sodium hydrogen carbonate.

The amine of the general formula (V), and the general formula (V
The carboxylic acid derivative of I) is produced by a known method.

The thus obtained compound represented by the general formula (I) according to the present invention is generally mixed with an inert liquid carrier or a solid, and is in a commonly used formulation form such as powder, granules and hydration. It is used by preparing it as a drug, emulsion, flowable agent, etc. Further, an auxiliary agent can be added if necessary for formulation.

The carrier may be either solid or liquid, as long as it is usually used for agricultural and horticultural chemicals, and is not limited to a particular carrier. For example, solid carriers include clay, talc, bentonite,
Examples thereof include mineral powders such as calcium carbonate, diatomaceous earth, and white carbon, vegetable powders such as soybean powder and starch, polymer compounds such as petroleum resin, polyvinyl alcohol and polyalkylene glycol, urea and waxes. Examples of the liquid carrier include various organic solvents such as xylene, methylnaphthalene, and alkylbenzene, various oils such as vegetable oil, and water.

As the auxiliary agent, a surfactant, a binder (eg, lignin sulfonic acid, alginic acid, polyvinyl alcohol, gum arabic, CMC sodium, etc.) usually used for agricultural and horticultural agents, a stabilizer (eg, antioxidant) For example, a phenolic compound, a thiol compound or a high fatty acid ester may be used, a phosphate may be used as a pH adjuster, and a light stabilizer may be used), or the like, if necessary, and these may be used alone or in combination. Further, in some cases, an industrial bactericidal agent, an antibacterial and antifungal agent, etc. may be added for antibacterial and antifungal agents.

As examples of the surfactant, nonionic, anionic, cationic and amphoteric surfactants can be used alone or as a mixture. As the nonionic, those obtained by adding alkylphenol, higher alcohol, alkylnaphthol, higher fatty acid, fatty acid ester or the like to ethylene oxide (such as X-77 or Neugen EA80) or propylene oxide are preferable. Examples of anionic compounds include alkylphenols, alkylnaphthols, higher alcohols, higher fatty acids, fatty acid esters, etc., which have been converted to alkyl sulfonates (such as neoperex), alkyl sulfate ester salts, phosphate ester salts, etc. preferable. Further, lignin sulfonate (such as sun extract) is one of the preferable examples.

The content of the compound represented by the formula (I) in the herbicide according to the present invention varies depending on the formulation form, but it is usually 0.01 to 20% by weight in a powder and 1 in a wettable powder.
-50% by weight, 0.01-10% by weight for granules, 0.1-50% by weight for emulsions, 0.1-5 for flowable formulations
0% by weight, 1 to 50% by weight in a dry flowable formulation, preferably 0.1 to 3% by weight in powders, 10 to 40% by weight in wettable powders, 0.1 to 5% by weight in granules ,
1-30% by weight for emulsions, 1-30 for flowable formulations
% By weight, and 10-40% by weight for dry flowable formulations.

The content of the auxiliary agent is 0 to 80% by weight,
The content of the carrier is 100% by weight minus the contents of the active ingredient compound and the auxiliary agent.

The herbicide of the present invention represented by the formula (I) is
One or more other herbicides, or pesticides such as fungicides, insecticides and plant growth regulators, fertilizers, soil conditioners and the like can be mixed and used, and mixed preparations with them It is also possible, and a synergistic effect can be expected in some cases.

[0037]

EXAMPLES Next, the production method of the compound of the present invention will be specifically explained with reference to examples.

Example 1 Synthesis of 3,4-trans-4-ethyl-3- (3-fluorophenyl) -1- (3-isopropylphenyl) -2-pyrrolidinone [Compound No.-1] In 10 ml of dimethylformamide, 3,4-trans-
4-Ethyl-3- (3-fluorophenyl) -1- (4
1.0 g of -chloro-3-isopropylphenyl) -2-pyrrolidinone, 2.0 ml of formic acid and 0.7 g of 5% -palladium carbon were added, and the mixture was stirred at reflux temperature for 6 hours.
After the palladium carbon was filtered off, it was extracted with toluene. After drying over anhydrous sodium sulfate, the product was concentrated by an evaporator to quantitatively obtain the target compound.

Example 2 Synthesis of 3,4-trans-4-ethyl-3- (3-chlorophenyl) -1- (3-isopropylphenyl) -2-pyrrolidinone [Compound No.-
4] N- (2-butenyl) -N- (3
-Isopropylphenyl) -2-chloro-2- (3-chlorophenyl) acetamide (1.5 g) was added, and tributyltin hydride (1.2 g) and α, while stirring at reflux temperature.
A small amount of α-azobisisobutyronitrile (AIBN) was added. After stirring for 10 minutes, return to room temperature and
0.3 ml was added and the mixture was further stirred for 5 minutes. The reaction solution was concentrated with an evaporator and column chromatography was performed to obtain 0.9 g of the target compound.

Other compounds represented by the general formula (I) according to the present invention were synthesized in the same manner as in Example 1. The physical properties of the compound represented by formula (I) according to the present invention will be described below.

3,4-trans-4-ethyl-3- (3
-Fluorophenyl) -1- (3-isopropylphenyl) -2-pyrrolidinone [Compound No.-1] IR nunujol (cm ^-1 ): 1695 NMR (CDCl ₃ ) δppm: 0.97 (3H, t, J = 7.3Hz), 1.26 (6H, d, J =
6.8Hz), 1.51 ~ 1.62 (1H, m), 1.70 ~ 1.80 (1H, m), 2.38 ~ 2.
50 (1H, m), 2.86 ~ 2.96 (1H, m), 3.48 (1H, d, J = 10.4Hz), 3.5
8 (1H, t, J = 9.2Hz), 4.01 (1H, t, J = 9.2Hz), 6.96-7.07 (4H,
m), 7.25 to 7.41 (3H, m), 7.57 to 7.64 (1H, m) mp 58.5 to 60.0 ° C

3,4-trans-4-ethyl-3-
(3,5-Difluorophenyl) -1- (3-isopropylphenyl) -2-pyrrolidinone [Compound No.-2] IRνneat (cm ⁻¹ ): 1699 NMR (CDCl ₃ ) δppm: 0.98 (3H, t, J = 7.3Hz), 1.26 (6H, d, J =
6.8Hz), 1.51 to 1.58 (1H, m), 1.70 to 1.77 (1H, m), 2.37 to 2.
42 (1H, m), 2.89 ~ 2.94 (1H, m), 3.44 (1H, d, J = 10.3Hz), 3.5
8 (1H, t, J = 8.8Hz), 3.98 (1H, t, J = 8.8Hz), 6.98 ~ 7.39 (6H,
m), 7.55 ~ 7.64 (1H, m)

3,4-trans-4-ethyl-3-
(3,4-Difluorophenyl) -1- (3-isopropylphenyl) -2-pyrrolidinone [Compound No.-3] IRνnujol (cm ^-1 ): 1687 NMR (CDCl ₃ ) δPPM: 0.98 (3H, t, J = 7.3Hz), 1.26 (6H, d, J =
6.6Hz), 1.53 to 1.60 (1H, m), 1.72 to 1.77 (1H, m), 2.40 to 2.
44 (1H, m), 2.89 ~ 2.96 (1H, m), 3.47 (1H, d, J = 10.3Hz), 3.5
8 (1H, t, J = 9.2Hz), 3.99 (1H, t, J = 9.2Hz), 6.72-6.85 (3H,
m), 7.04 to 7.55 (3H, m), 7.61 to 7.63 (1H, m) mp 77.0 to 79.0 ° C

3,4-trans-4-ethyl-3- (3
-Chlorophenyl) -1- (3-isopropylphenyl) -2-pyrrolidinone [Compound No.-4] IRνnujol (cm ^-1 ): 1704 NMR (CDCl ₃ ) δppm: 0.97 (3H, t, J = 7.6Hz), 1.26 (6H, d, J =
6.6Hz), 1.50 ~ 1.61 (1H, m), 1.71 ~ 1.78 (1H, m), 2.41 ~ 2.
50 (1H, m), 2.92 (1H, sept, J = 6.6Hz), 3.46 (1H, d, J = 10.3H
z), 3.58 (1H, t, J = 9.2Hz), 4.11 (1H, t, J = 9.2Hz), 7.05 (1H,
d, J = 8.0Hz), 7.16 (1H, d, J = 7.3Hz), 7.22〜7.41 (5H, m), 7.
64 (1H, d, J = 2.2Hz) .mp 88.5-90.0 ℃

3,4-trans-4-ethyl-3- (3
-Bromophenyl) -1- (3-isopropylphenyl) -2-pyrrolidinone [Compound No.-5] IRνKbr (cm ^-1 ): 1700 NMR (CDCl ₃ ) δppm: 0.97 (3H, t, J = 7.6Hz), 1.21 (6H, d, 6.6H
z), 1.52 ~ 1.59 (1H, m), 1.71 ~ 1.76 (1H, m), 2.2.38 ~
2.50 (1H, m), 2.89 ~ 2.94 (1H, m), 3.45 (1H, d, J = 10.3Hz),
3.57 (1H, dd, J = 8.8Hz, 9.5Hz), 4.00 (1H, dd, J = 8.1Hz, 8.8H
z), 7.04 (1H, d, J = 7.3Hz), 7.15〜7.43 (6H, m), 7.64 (1H, s) mp 82.0〜83.2 ℃

A synthetic example of an important intermediate for synthesizing the compound of the general formula (I) of the present invention will be described below as a reference example.

Reference Example 1 3,4-trans-4-ethyl-3- (3-fluorophenyl) -1- (4-chloro-
Synthesis of 3-isopropylphenyl) -2-pyrrolidinone N- (2-butenyl) -N- (4
-Chloro-3-isopropylphenyl) -2-chloro-
2.0 g of 2- (3-fluorophenyl) acetamide was added, and 1.8 g of tributyltin hydride and α, α-azobisisobutyronitrile (AI) were added with stirring at the reflux temperature.
BN) A very small amount was added. After stirring for 10 minutes, the temperature was returned to room temperature, 0.3 ml of DBU was added, and the mixture was further stirred for 5 minutes. The reaction solution was concentrated with an evaporator and column chromatography was performed to obtain 1.4 g of the target compound.

In the same manner as in Reference Example 1, the general formula (II
Other pyrrolidinone derivatives represented by I) were synthesized. The physical properties of the compound represented by formula (III) are shown below. 3,4-trans-4-ethyl-3- (3-fluorophenyl) -1- (4-chloro-3-isopropylphenyl) -2-pyrrolidinone IRνneat (cm ⁻¹ ): 1702 NMR (CDCl ₃ ) δppm: 0.97 (3H, t, J = 7.2Hz), 1.21〜1.27 (6
H, m), 1.50 ~ 1.60 (1H, m), 1.70 ~ 1.80 (1H, m), 2.40 ~ 2.5
0 (1H, m), 3.35 ~ 3.45 (1H, m), 3.48 (1H, d, J = 10.4Hz), 3.54
(1H, t, J = 8.8Hz), 3.99 (1H, t, J = 8.8Hz), 6.96 ~ 7.06 (3H,
m), 7.26 ~ 7.37 (3H, m), 7.76 (1H, s)

3,4-trans-4-ethyl-3-
(3,5-Difluorophenyl) -1- (4-chloro-
3-Isopropylphenyl) -2-pyrrolidinone IRνneat (cm ⁻¹ ): 1702 n _D 22.2 ° C .: 1.5398

3,4-trans-4-ethyl-3-
(3,4-Difluorophenyl) -1- (4-chloro-
3-Isopropylphenyl) -2-pyrrolidinone IRνneat (cm ⁻¹ ): 1701 n _D 23.1 ° C .: 1.5670

Reference Example 2 N- (2-butenyl) -N-
Synthesis of (4-chloro-3-isopropylphenyl) -2-chloro-2- (3-fluorophenyl) acetamide In 40 ml of N, N-dimethylformamide, N- (2-
Butenyl) -N- (4-chloro-3-isopropylphenyl) amine (2.2 g) and anhydrous potassium carbonate (2.0 g) were added,
2.6 g of 2-chloro-2- (3-fluorophenyl) acetyl chloride was gradually added dropwise at 20 to 30 ° C while stirring. After continuing stirring for another 20 minutes, potassium carbonate was filtered off and extracted with toluene. After drying over anhydrous sodium sulfate, the product was concentrated with an evaporator to quantitatively obtain the target oily substance.

In the same manner as in Reference Example 2, the compound of the general formula (IV)
Other amide derivatives represented by were synthesized. less than,
The physical properties of the compound represented by formula (IV) are described below.

N- (2-butenyl) -N- (4-chloro-3-isopropylphenyl) -2-chloro-2- (3
-Fluorophenyl) acetamide IRνneat (cm ^-1 ): 1679 n _D 32.1 ° C: 1.5502

N- (2-butenyl) -N- (4-chloro-3-isopropylphenyl) -2-chloro-2-
(3,5-Difluorophenyl) acetamide IRνneat (cm ^-1 ): 1680 n _D 24.6 ° C: 1.5175

N- (2-butenyl) -N- (4-chloro-3-isopropylphenyl) -2-bromo-2-
(3,4-Difluorophenyl) acetamide IRνneat (cm ^-1 ): 1677 n _D 24.2 ° C: 1.5497

N- (2-butenyl) -N- (3-isopropylphenyl) -2-chloro-2- (3-chlorophenyl) acetamide IRνneat (cm ^-1 ): 1676 n _D 21.4 ° C .: 1.5617

Reference Example 3 N- (2-butenyl) -N-
Synthesis of (4-chloro-3-isopropylphenyl) amine In 15 ml of N, N-dimethylformamide, 3.2 g of 4-chloro-3-isopropylaniline, 2.8 g of anhydrous potassium carbonate and 1-chloro-2-butene 2 were added. 0.0 g was added, and the mixture was stirred at 70 to 90 ° C. for 1 hour. After the potassium carbonate was filtered off, 100 ml of water was added and the mixture was extracted with toluene. After drying over anhydrous sodium sulfate, the product was concentrated with an evaporator and subjected to silica gel column chromatography to obtain 1.5 g of the desired compound.

IRνneat (cm ^-1 ): 3418 n _D 23.0 ° C .: 1.5145

In a similar manner, N- (2-butenyl)
-N- (3-isopropylphenyl) amine was synthesized.

IRνneat (cm ⁻¹ ): 3413 n _D 21.4 ° C .: 1.5303

Reference Example 4 3,4-cis-4-ethyl-3
Synthesis of-(3-chlorophenyl) -1- (3-isopropylphenyl) -2-pyrrolidinone [Compound No.-6] N- (2-butenyl) -N- (3 in 15 ml of toluene.
2.0 g of -isopropylphenyl) -2-chloro-2- (3-chlorophenyl) acetamide was added, and 1.7 g of tributyltin hydride and α, while stirring at reflux temperature.
A small amount of α-azobisisobutyronitrile (AIBN) was added. After continuing stirring for 10 minutes, the temperature was returned to room temperature, and the reaction solution was concentrated with an evaporator. By column chromatography, the first eluted compound, 3,4
-Trans-4-ethyl-3- (3-chlorophenyl)
0.9 g of -1- (3-isopropylphenyl) -2-pyrrolidinone [Compound No.-4], and the compound eluted later, 3,4-cis-4-ethyl-3- (3
0.3 g of -chlorophenyl) -1- (3-isopropylphenyl) -2-pyrrolidinone [Compound No.-6] was obtained.

3,4-cis-4-ethyl-3- (3-chlorophenyl) -1- (3-isopropylphenyl)-
Physical properties of 2-pyrrolidinone [Compound No.-6] IRνnujolcm ⁻¹ : 1702 .NMR (CDCl ₃ ) δPPM: 0.91 (3H, t, J = 7.6Hz), 1.24 (6H, d, J =
6.6Hz), 1.21 ~ 1.75 (2H, m) ,, 2.63 ~ 2.74 (1H, m), 2.80 ~
2.95 (1H, m,), 3.69 (1H, dd, J = 7.4Hz, 9.3Hz), 4.00 (1H, d, J =
8.9Hz), 4.03 (1H, dd, J = 7.3Hz, 9.3Hz), 7.03 (1H, d, J = 8.0H
z), 7.13 (1H, d, J = 7.3Hz), 7.20 ~ 7.66 (6H, m)

The configuration of the 3-position and 4-position of the pyrrolidinone ring is the bond between the proton of 3-position of the pyrrolidinone ring (indicated as 3-H) and the proton of 4-position of the pyrrolidinone ring (indicated as 4-H). Determined by a constant. That is, in the case of 4-ethyl-3- (3-chlorophenyl) -1- (3-isopropylphenyl) -2-pyrrolidinone, J _{3H-4 H}
The value of = 10.3 Hz is 3,4-transformer, J
Those showing a value of _3H-4H = 8.9 Hz are determined to be 3,4-cis isomers.

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 (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, Sanyo Kasei) Made; polyoxyethylene nonyl phenyl ether): 1
Parts by weight, white carbon: 5 parts by weight and diatomaceous earth 72
A wettable powder was obtained by thoroughly pulverizing and mixing parts by weight.

Formulation Example 2 (Wettable powder) Compound (2) of the present invention: 20 parts by weight, sodium alkylbenzene sulfonate: 2 parts by weight, polyoxyethylene alkylphenyl ether: 1 part by weight, and sikhlite:
A wettable powder was obtained by thoroughly pulverizing and mixing 77 parts by weight.

Formulation Example 3 (Wettable powder) Compound (3) of the present invention: 50 parts by weight, white carbon:
5 parts by weight, polyoxyethylene alkylphenyl ether ammonium sulfate salt: 6 parts by weight, sodium lignin sulfonate: 2 parts by weight and diatomaceous earth: 37 parts by weight
A wettable powder was obtained by pulverizing and mixing using an et-0-mizer.

Formulation Example 4 (flowable agent) Inventive compound (1): 5 parts by weight, sodium lignin sulfonate: 2 parts by weight, xanthan gum: 0.3 part by weight and polyoxyethylene alkylaryl ether: 1 part by weight, Water: 91.7 parts by weight was added and mixed, and then finely pulverized using a sand grinder to obtain a flowable agent.

Formulation Example 5 (flowable agent) Compound (2) of the present invention: Sun extract P252 (trade name, the same as above) dissolved in 30 parts by weight of water and 50 parts by weight of water: 10
Kelzan S (trade name, manufactured by Kelco; xanthan gum) dissolved in 9.6 parts by weight of water after wet-pulverizing and mixing parts by weight: 0.2 part by weight and Deltop (trade name, manufactured by Takeda Pharmaceutical Co., Ltd .: organic iodine type) Antifungal agent): 0.2 parts by weight were added and mixed to obtain a flowable agent.

Formulation Example 6 (Dust) 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 well pulverized and mixed to obtain a dust.

Formulation Example 7 (powder) Compound (4) 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 are mixed and pulverized. A powder was obtained.

Formulation Example 8 (Dry flowable agent) Finely ground compound (3) of the present invention: 60 parts by weight, sodium alkylbenzenesulfonate: 5 parts by weight and polypropylene glycol polyethylene glycol ether: 3
5 parts by weight were mixed to obtain a dry flowable agent.

Formulation Example 9 (Granule) Compound (1) of the present invention: 0.3 part by weight, Neoperex (trade name, the same as above): 2 parts by weight, Sun Extract P25
2 (trade name, manufactured by Sanyo Kokusaku Pulp; sodium lignin sulfonate): 2 parts by weight, bentonite: 72.7 parts by weight and talc: 23 parts by weight, were mixed well, and then an appropriate amount of water was added to moisten the mixture. It was extruded and granulated with a small injection molding machine. This was air-dried at 30 to 60 ° C. and crushed, and then granulated to 0.3 to 2 mm with a granulator to obtain granules.

Formulation Example 10 (Granule) 0.5 part by weight of the compound (4) of the present invention, gohsenol (G
Osenol) GL-05s (Nippon Gosei Kagaku PV
A): 2 parts by weight, Sun Extract P252 (Sanyo Kokusaku Pulp Sodium Benzenesulfonate): 2 parts by weight and clay:
After thoroughly mixing 95.5 parts by weight, an appropriate amount of water was added to wet the mixture, and the mixture was extruded and granulated by an injection molding machine. This is air-dried at 60 to 90 ° C and crushed, and then 0.3 to 1 by a sizing machine.
The particle size was adjusted to mm to obtain a granule.

Formulation Example 11 (Emulsion) Compound (3) of the present invention: 10 parts by weight, Solpol 800
A (trade name, manufactured by Toho Kagaku; 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.

Physiological Test Examples Test Example 1 Flooded soil treatment (pre-emergence treatment) 1/5000 arengren pots were filled with soil, and seeds of Taenia muscaria, firefly, konjac, and azena were sown to make a flooded state. Rice seedlings (2-
(3 leaves stage) 2 strains were set as 1 strain, and the 2 strains were transplanted and grown in a greenhouse. One day later (before the occurrence of weeds), a predetermined amount of the test composition was treated with granules prepared according to the method described in Formulation Example 9 above, and after 30 days, the condition of weeds and phytotoxicity to paddy rice were treated. The situation was observed and investigated. The result is first
The results are shown in Tables (Table 1) and (Table 2). In the table, the degree of damage to the test plant and the degree of chemical damage to paddy rice are shown based on the following criteria in comparison with the wind dry weight in the case of no treatment.

[0077] Growth rate (%) shown by air dry weight ratio to the untreated plot 50 to 5 (wither) 4 6 to 10 (severe damage) 3 11 to 40 (intermediate damage) 2 41 to 70 (small damage) 171 to 90 (slightly harmed) 091 to 100 (harmless) Comparative compounds A, B and C represent the following compounds.
(Same for Test Example 2) A: 1- (3-trifluoromethylphenyl) -3-chloro-4-chloromethyl-2-pyrrolidinone B: 4-chloromethyl-3- (3-chlorophenyl)-
1- (3-trifluoromethylphenyl) -2-pyrrolidinone C: 4-ethyl-3- (3-fluorophenyl) -1-
(3-trifluoromethylphenyl) -2-pyrrolidinone

[0078]

[Table 1]

[0079]

[Table 2]

In this test, the herbicide according to the present invention was
Compared to the comparative agents A, B, and C, even in the low-dose treatment, it showed a high herbicidal effect against the paddy field weeds tested, and showed excellent safety against paddy rice. Further, the isomer [Compound No. 6] of the compound of the present invention showed almost no herbicidal effect.

Test Example 2 Submerged Soil Treatment (Growth Stage Treatment) The soil was filled in a 1/5000 arenagner pot and seeds of Tainubie, firefly, konagi, and azena were sown to make a submerged state. Rice seedlings (2-
(3 leaves stage) 2 strains were set as 1 strain, and the 2 strains were transplanted and grown in a greenhouse. When the leaf was transformed into two leaves, a predetermined amount of the test composition was treated with a granule prepared according to the method described in the above Preparation Example 10, and after 30 days, the occurrence of weeds and phytotoxicity to paddy rice. The situation was observed and investigated. The results are shown in Table 2 (Table 3) and (Table 4). In the table, the degree of damage to the test plant and the degree of phytotoxicity to paddy rice are shown in the same manner as in Test Example 1.

[0082]

[Table 3]

[0083]

[Table 4]

In this test, the herbicide according to the present invention was
Compared to the comparative agents A, B, and C, even in the low-dose treatment, it showed a high herbicidal effect against the paddy field weeds tested, and showed excellent safety against paddy rice. The isomer of the compound of the present invention [Compound No. 6] showed almost no herbicidal effect.

[0085]

The 3,4-trans-4-ethyl-3- (substituted phenyl) represented by the general formula (I) according to the present invention
The -1- (3-isopropylphenyl) -2-pyrrolidinone derivative is a novel compound, and the herbicide containing the compound of the present invention is useful for the growth of various weeds that are problematic in paddy fields before and after the outbreak. It shows herbicidal activity at low dose until the end of the period. It also has excellent selectivity for rice and can be used safely.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Toru Miura             1144 Togo, Mobara-shi, Chiba Mitsui Toatsu Chemical Co., Ltd.             Inside the company (72) Inventor Makoto Nishida             1144 Togo, Mobara-shi, Chiba Mitsui Toatsu Chemical Co., Ltd.             Inside the company (72) Inventor Sachiko Hibi             1144 Togo, Mobara-shi, Chiba Mitsui Toatsu Chemical Co., Ltd.             Inside the company

Claims (2)

[Claims] 1. General formula (I) (Chemical formula 1) (In the formula, X represents a fluorine atom substituted at the 3-position, a chlorine atom, a bromine atom, a fluorine atom substituted at the 3-position and 4-position, or a 3-position and the 5-position). , 4-trans-4-ethyl-3- (substituted phenyl) -1- (3
-Isopropylphenyl) -2-pyrrolidinone derivative. 2. The general formula (I) (Chemical Formula 2) (In the formula, X represents a fluorine atom substituted at the 3-position, a chlorine atom, a bromine atom, a fluorine atom substituted at the 3-position and 4-position, or a 3-position and the 5-position). , 4-trans-4-ethyl-3- (substituted phenyl) -1- (3
-Isopropylphenyl) -2-pyrrolidinone derivative.