JPH09124596A - New 3-pyrrolin-2-one derivative and herbicide containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound represented by a specific formula, not giving damage to rice in a paddy field, having a wide range of weeding spectrum at a low dose and usable over a wide period and useful as a selective herbicide. SOLUTION: This compound is represented by formula I [X is H or F; Y is a halogen; (n) is 1 or 2], e.g. 1-[1-methyl-1-(4-chloronaphtalen-2-yl)ethyl]-4- methyl-3-phenyl-3-pyrrolin-2-one. Furthermore, the compound is preferably obtained by treating, e.g. an amide derivative of formula II with a base such as sodium hydroxide in a solvent such as ethyl acetate at -70 to 170 deg.C, and a compound obtained by treating an aminoketone derivative of formula III and a carboxylic acid derivative of formula IV (Q is a halogen) with a base such as pyridine in a solvent such as dichlorobenzene is preferably used as the derivative of formula II.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to novel 3-pyrrolin-2-one derivatives and herbicides containing these as active ingredients.

[0002]

2. Description of the Related Art Some 3-pyrroline derivatives having herbicidal activity have been disclosed so far. For example, in JP-A-3-204855, the following general formula (Formula 3)

[0003]

Embedded image The compound represented by is disclosed as a herbicide.

Further, Japanese Patent Laid-Open No. 6-25160 discloses that
The following general formula (Formula 4)

[0005]

Embedded image (In the formula, R ₁ is an optionally substituted phenyl group, and R 1
₂ is an alkyl group which may be substituted with a hydrogen atom or a halogen atom, and R ₃ is an optionally substituted thiophene, furan, pyrrole, benzofuran, benzothiophene, indole, benzoxazole, benzothiazole or benzimidazole group. Indicates a heterocycle. ) Are disclosed as herbicides. The pyrroline compounds disclosed in these prior arts have extremely high activity when used in paddy fields, and exhibit a broad herbicidal spectrum. However, if there is some kind of external factor, for example, downward movement of water due to water leakage or the like, it causes significant phytotoxicity to paddy rice, which makes it difficult to use in actual fields.

In recent years, there has been a strong demand for a highly selective herbicide which does not harm crops and kills only weeds.
Further, in paddy fields, effective herbicides that can reliably control difficult-to-control weeds such as barnyard grass, fireflies, puppies, and sedges are desired. Furthermore, there is a strong demand for the development of a herbicide which can be used for any period from the time of emergence of weeds to the growing season and has a long-lasting effect. In such a situation, there is a problem in the actual paddy field that there are various external factors that affect the effects and phytotoxicity of the herbicide. For example, the external factors include soil quality of paddy fields, weather conditions such as temperature and light, inundation depth, water leakage, or inflow,
Water migration due to runoff and sometimes differences in planting depth of rice, etc., but these factors are singly or intricately entangled with each other, which may affect the effects of the drug on weeds, phytotoxicity on crops, or stability of effect. It causes great fluctuations. The most important of these variables is the effect of water leakage. In many leaky fields, the use of herbicides must be severely restricted due to the occurrence of phytotoxicity caused by downward movement of water and chemicals, or fluctuation of the effect.

[0007]

Therefore, the present invention does not harm rice in a paddy field, has a wide spectrum of weeding with a low dose, and has a wide range from pre-emergence to post-emergence growth. An object of the present invention is to provide a selective herbicide which can be used for a period of time, and whose effects and phytotoxicity are not changed even by external factors such as water leakage.

[0008]

Means for Solving the Problems The present inventors have conducted research on 3-pyrroline derivatives in order to solve the above-mentioned problems, and as a result, a novel 3-pyrroline-2-one derivative is extremely excellent as a herbicide, and It has been found that it has excellent characteristics that it does not cause phytotoxicity to rice, which is a useful crop, and that its effects and phytotoxicity do not fluctuate due to external factors such as water leakage.

That is, the present invention relates to the general formula (I)

[0010]

Embedded image (In the formula, X represents a hydrogen atom or a fluorine atom, Y represents a halogen atom, and n represents 1 or 2.), and a 3-pyrrolin-2-one derivative represented by the formula It is a characteristic herbicide.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The 3-pyrrolin-2-one derivative of the present invention is a novel compound and can be produced by the method represented by the reaction formula (1).

[0012]

[Chemical 6] That is, the amide derivative represented by the general formula (II) (wherein X represents a hydrogen atom or a fluorine atom, Y represents a halogen atom, and n represents 1 or 2) is treated with a suitable base. Then, it can be produced by advancing an intramolecular aldol condensation reaction.

Suitable bases used in this reaction include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide, and metals. Alkali metals such as sodium, potassium metal and lithium, metal hydrides such as sodium hydride and lithium hydride, alcoholates such as potassium t-butoxide and sodium alkoxide, picoline, quinoline and 1,8-diazabicyclo [5. 4.0] Organic bases such as undecene-7 (DBU). This reaction can be carried out in a suitable solvent or without solvent. 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 aprotic solvents such as dimethylformamide and dimethylacetamide. The reaction temperature is -70 to 170 ° C, and the reaction may be carried out at the reflux temperature of the solvent.

The amide derivative represented by the general formula (II) is produced by the method represented by the reaction formula (2).

[0015]

Embedded image That is, the aminoketone derivative represented by the general formula (III) (wherein Y and n have the same meanings as described above) and the carboxylic acid derivative represented by the general formula (IV) (wherein X is the above-mentioned). And Q represents a halogen atom.) In the presence of a suitable base.
The reaction is carried out without solvent or in a suitable solvent. Suitable solvents include aromatics such as benzene, toluene, xylene, chlorobenzene and dichlorobenzene, halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride, ethers such as diethyl ether, tetrahydrofuran and dioxane, and ethyl acetate. And esters such as butyl acetate. Suitable bases are triethylamine, pyridine, dimethylaniline, diisobutylethylamine, sodium hydrogencarbonate, potassium hydrogencarbonate, potassium carbonate, sodium carbonate, etc., and the reaction proceeds at any temperature.

The aminoketone derivative represented by the general formula (III) is synthesized by the method represented by the reaction formula (3).

[0017]

Embedded image That is, 1-methyl-1- represented by the general formula (V)
(Halogenonaphthalen-2-yl) ethylamine derivative (in the formula, Y and n have the same meanings as described above), and a halogenoacetone derivative represented by the general formula (VI) (in the formula, Z
Represents a halogen atom. ) Is produced.

In producing the compound of the present invention,
1-Methyl-1-represented by the general formula (V) as an intermediate
The (halogenonaphthalen-2-yl) ethylamine derivative can be produced by the following reaction formula (4).

[0019]

Embedded image (In the formula, Y and n have the same meanings as described above, and W represents a halogen atom.) That is, a 2-halogenomethylnaphthalene derivative (general formula (VII)) is cyanated to give a 2-cyanomethylnaphthalene derivative (general). Formula (VIII)) is obtained and the 2-methyl-2- (halogenonaphthalen-2-yl) propionitrile derivative (general formula (IX)) is obtained by dimethylation,
By hydrolyzing this compound, an amide derivative (general formula (X)) can be obtained, and 1-methyl-1- (halogenonaphthalen-2-yl) ethylamine represented by the general formula (V) can be obtained by Hoffmann reaction. it can.

The 2-methylhalogenonaphthalene derivative or the (halogenonaphthalen-2-yl) carboxylic acid derivative which is a raw material of the 2-halogenonaphthalene derivative is described in JP-A-2-202864 or Journal of Medicinal Chemistry, 1993, 36, 24
85-2493 (J. Med. Chem. 1993, 3).
6, 2485-2493) and the like.

The herbicide containing the compound of the present invention thus obtained as an active ingredient has, as its action characteristics, harmful weeds which are problematic in most paddy fields, for example, grass weeds such as Nobie, Cyperaceae such as Cyperaceae and Firefly. It has an excellent herbicidal effect on annual broadleaf weeds such as weeds and eels, and perennial weeds such as Urikawa. On the other hand, it does not show phytotoxicity to rice, a useful crop. Further, the herbicides relating to the compound of the present invention, in all treatment methods such as water-resisting soil treatment, soil treatment, soil admixture treatment, from the generation period of weeds to the growth period after generation, over a wide period,
Can be used effectively.

The compound of the present invention is 1-methyl-1- (halogenonaphthalen-2-yl) at the 1-position of the pyrroline ring.
In terms of the presence of an ethyl group, the above-mentioned prior arts (JP-A-3-204855 and JP-A-6-25160).
No.). In improving the performance as a herbicide, 1-methyl-1- at the 1-position of the pyrroline ring
The presence of the (halogenonaphthalen-2-yl) ethyl group has a great significance, and when the compound of the present invention is treated as a herbicide, almost no phytotoxicity occurs even in the presence of water leakage, as is clear from the test examples described below. Moreover, the fluctuation of the effect is hardly observed, and it can be safely used with a high effect even in a leaky field. In addition, there is little phytotoxicity during shallow planting of rice, which is usually seen in general chemical treatment. Further, the position of the halogen atom on the naphthalene ring is preferably 1-position, 4-position, 5-position and 8-position, and more preferably 4-position.

When the compound represented by the general formula (I) according to the present invention is used as a herbicide, it is generally mixed with an inert liquid carrier or a solid to prepare a powder, granule, Used as a wettable powder, emulsion, flowable agent, etc. If necessary for the preparation, an auxiliary agent can be added. The carrier may be either solid or liquid as long as it is usually used for agricultural and horticultural agents, and is not limited to a particular carrier.

Examples of the solid carrier include clay, talc, bentonite, calcium carbonate, white carbon, mineral powder such as diatomaceous earth, soybean powder, vegetable powder such as starch, petroleum resin, polyvinyl alcohol, polyalkylene glycol and the like. Polymer compounds such as urea,
Examples thereof include waxes. Examples of the liquid carrier include various organic solvents such as xylene, methylnaphthalene, alkylbenzene, halogenated benzene, various oils such as vegetable oil, and water.

As the auxiliary agent, a surfactant, a binder (for example, lignin sulfonic acid, alginic acid, polyvinyl alcohol, gum arabic, CMC sodium, etc.) usually used for agricultural and horticultural chemicals, a stabilizer (for example, for antioxidant) A phenolic compound, a thiol compound or a high fatty acid ester, a phosphate as a pH adjuster, and sometimes a light stabilizer are also used), if necessary, alone or in combination. Further, in some cases, an industrial bactericide, a bactericidal / antifungal agent, etc. can be added for bactericidal / fungicidal purposes.

As examples of the surfactant, nonionic, anionic, cationic and amphoteric surfactants can be used alone or in combination. As the nonionic, those obtained by adding ethylene oxide or propylene oxide to alkylphenol, higher alcohol, alkylnaphthol, higher fatty acid, fatty acid ester and the like are preferable. As the anionic one, alkyl phenol, alkyl naphthol, higher alcohol, higher fatty acid, fatty acid ester and the like are preferably converted into alkyl sulfonate, alkyl sulfate, phosphate and the like. In addition, lignin sulfonate and the like are also mentioned as one of the preferable ones.

The content of the compound represented by the general 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 for powders and 1 to 50% by weight for wettable powders. 0.01-10% by weight for agents, 0.1 for emulsions
% To 50% by weight, 0.1 to 50% by weight for flowable preparations, 1 to 50% by weight for dry flowable preparations, preferably 0.1 to 3% by weight for powders, 10 to 40% by weight for wettable powders, and 10 to 40% by weight for granules. 0.1-5% by weight, emulsion 1-30% by weight,
It is 1 to 30% by weight in the flowable formulation and 10 to 40% by weight in the dry flowable formulation. The content of the auxiliary agent is 0 to 80% by weight, and the content of the carrier is 100% by weight minus the contents of the active ingredient compound and the auxiliary agent.

The application amount of the herbicide of the present invention varies depending on the condition of weeds generation, environment, or formulation form used, but it is 0.00 per hectare of the active ingredient of the compound.
It is good to select from the range of 5 to 2 kg, preferably 0.01 to 1 kg, and more preferably 0.025 to 0.4 kg.

The herbicide of the present invention represented by the general formula (I) is one or more of the other herbicides, or pesticides such as fungicides, insecticides and plant growth regulators, fertilizers, soil conditioners, etc. Of course, it can be used mixed with
A mixed preparation with these is also possible, and a synergistic effect can be expected in some cases.

[0030]

EXAMPLES Next, the production method of the compound of the present invention will be specifically described with reference to Examples, and reference will be made to Synthesis Examples of important intermediates for synthesizing the compound of the general formula (I) of the present invention.
In addition, formulation examples and herbicidal activity test examples of the herbicide according to the present invention are shown.

Example 1 1- [1-methyl-1- (4-chloronaphthalene-2-
Synthesis of (yl) ethyl] -4-methyl-3-phenyl-3-pyrrolin-2-one (Compound No.-1) N- [1-Methyl-1-in 20 ml of dichloromethane.
(4-Chloronaphthalen-2-yl) ethyl] -N-
(2-Oxopropyl) amine 1.0 g and pyridine 1.2 g were added, and phenylacetic acid chloride 1.2 was added at room temperature.
g was added dropwise. After continuously stirring for 5 hours, a saturated aqueous solution of sodium hydrogen carbonate was added and the mixture was extracted with dichloromethane. After drying over anhydrous sodium sulfate, the mixture was concentrated with an evaporator, and the obtained oil was dissolved in 20 ml of ethyl acetate. 28% methanol solution of sodium methylate 10
After adding ml, stirring under reflux for 15 minutes, returning to room temperature, adding water and extracting with ethyl acetate. Wash with 4% aqueous hydrochloric acid and saturated aqueous sodium bicarbonate,
Dry over anhydrous sodium sulfate. By concentrating with an evaporator and performing silica gel column chromatography, 1- [1-methyl-1- (4-chloronaphthalen-2-yl) ethyl] -4-methyl-3-phenyl-3- of the present invention is obtained. 0.4 g of pyrrolin-2-one was obtained. IRν film cm-1: 1682.NMR (270MHz, CDCl ₃ ) δppm: 1.92 (6
H, s), 2.15 (3H, s), 3.98 (2H, s), 7.30 ~ 7.70 (9H, m), 7.81 ~
7.84 (1H, m), 8.18 ~ 8.21 (1H, m).

Example 2 In the same manner as in Example 1, 1- [1-methyl-1- (halogenonaphthalen-2-yl) ethyl] -4-methyl-3-phenyl-3 according to the present invention. -Pyrrolin-2-one derivatives were synthesized. The compound names, compound numbers, and physical properties are shown below.

1- [1-Methyl-1- (4-bromonaphthalen-2-yl) ethyl] -4-methyl-3-phenyl-3-pyrrolin-2-one (Compound No. 2) IRν film cm-1: 1677.NMR (270MHz, CDCl ₃ ) δppm: 1.93 (6H,
s), 2.16 (3H, s), 3.99 (2H, s), 7.28 ~ 7.58 (7H, m), 7.76 ~ 7.
83 (3H, m), 8.17 (1H, d, J = 8.8Hz).

1- [1-Methyl-1- (5-bromonaphthalen-2-yl) ethyl] -4-methyl-3-phenyl-3-pyrrolin-2-one (Compound No. 3) IRν film cm-1: 1676.NMR (270MHz, CDCl ₃ ) δppm: 1.95 (6H,
s), 2.15 (3H, s), 3.97 (2H, s), 7.28 ~ 7.39 (3H, m), 7.44 ~ 7.
48 (2H, dd, J = 1.5Hz, 8.1Hz), 7.61 ~ 7.65 (1H, dd, J = 2.2Hz,
8.8Hz), 7.72 ~ 7.80 (4H, m), 8.17 ~ 8.21 (1H, d, J = 8.8Hz).

1- [1-methyl-1- (8-chloronaphthalen-2-yl) ethyl] -4-methyl-3- (2-
Fluorophenyl) -3-pyrrolin-2-one (Compound No. 4) mp106.0-106.3 ° C. IRνKBr cm-1: 1671.NMR (270MHz, C
DCl ₃ ) δppm: 1.98 (6H, s), 2.02 (3H, s), 4.01 (2H, s), 7.05〜
7.18 (2H, m), 7.28〜7.45 (3H, m), 7.54〜7.62 (2H, m), 7.71
~ 7.74 (1H, d, J = 8.1Hz), 7.81 ~ 7.85 (1H, d, J = 8.8Hz), 8.18
~ 8.19 (1H, d, J = 1.5Hz).

1- [1-methyl-1- (5-chloronaphthalen-2-yl) ethyl] -4-methyl-3-phenyl-3-pyrrolin-2-one (Compound No. 5) IRν film cm-1: 1678.NMR (270MHz, CDCl ₃ ) δppm: 1.95 (6H,
s), 2.15 (3H, s), 3.98 (2H, s), 7.28〜7.80 (10H, m), 8.21〜
8.241 (1H, d, J = 8.8Hz).

1- [1-Methyl-1- (1-bromonaphthalen-2-yl) ethyl] -4-methyl-3-phenyl-3-pyrrolin-2-one (Compound No. 6) IRν film cm-1: 1675.NMR (270MHz, CDCl ₃ ) δppm: 1.94 (6H,
s), 2.22 (3H, s), 4.17 (2H, s), 7.14 to 7.52 (8H, m), 7.72 to 7.
84 (2H, m), 8.42 (1H, d, J = 8.8Hz).

1- [1-methyl-1- (6-fluoronaphthalen-2-yl) ethyl] -4-methyl-3-phenyl-3-pyrrolin-2-one (Compound No. 7) mp 135.0-138.0 ° C .IRνKBr cm-1: 1679.

1- [1-methyl-1- (6-fluoronaphthalen-2-yl) ethyl] -4-methyl-3- (2
-Fluorophenyl) -3-pyrrolin-2-one (Compound No. 8) mp 110.7-113.4 ° C. IRνKBr cm-1: 1683.

1- [1-Methyl-1- (8-chloronaphthalen-2-yl) ethyl] -4-methyl-3-phenyl-3-pyrrolin-2-one (Compound No. 9) mp 117.0-118.0 ° C .IRνKBr cm-1: 1677.

1- [1-Methyl-1- (7-chloronaphthalen-2-yl) ethyl] -4-methyl-3-phenyl-3-pyrrolin-2-one (Compound No. 10) IRν film cm-1: 1683.NMR (270MHz, CDCl ₃ ) δppm: 1.93 (6H,
s), 2.14 (3H, s), 3.96 (2H, s), 7.27 ~ 7.44 (5H, m), 7.47 ~ 7.
53 (2H, m), 7.67 ~ 7.80 (4H, m).

1- [1-Methyl-1- (6-chloronaphthalen-2-yl) ethyl] -4-methyl-3-phenyl-3-pyrrolin-2-one (Compound No. 11) mp 163.0-163.5 ℃ .IRνKBr cm-1: 1679.NMR (270MHz, C
DCl ₃ ) δppm: 1.94 (6H, s), 2.14 (3H, s), 3.96 (2H, s), 7.28〜
7.57 (7H, m), 7.70 ~ 7.78 (4H, m).

1- [1-methyl-1- (6,7-dibromonaphthalen-2-yl) ethyl] -4-methyl-3-
Phenyl-3-pyrrolin-2-one (Compound No. 12) IRν film cm-1: 1677. NMR (270MHz, CDCl ₃ ) δppm: 1.91 (6H, 6H,
s), 2.16 (3H, s), 3.99 (2H, s), 7.30 ~ 7.70 (8H, m), 8.09 (1H,
s), 8.12 (1H, s).

1- [1-Methyl-1- (6-bromonaphthalen-2-yl) ethyl] -4-methyl-3-phenyl-3-pyrrolin-2-one (Compound No. 13) mp 159.0-163.0 ° C .IRνKBr cm-1: 1679.

1- [1-methyl-1- (6-bromonaphthalen-2-yl) ethyl] -4-methyl-3- (2-
Fluorophenyl) -3-pyrrolin-2-one (Compound No. 14) IRν film cm-1: 1683. NMR (270MHz, CDCl ₃ ) δppm: 1.94 (6H, 6H,
s), 2.02 (3H, d, J = 2.2Hz), 3.99 (2H, s), 7.04 to 7.18 (2H, m),
7.22 ~ 7.44 (2H, m), 7.49 ~ 7.58 (2H, m), 7.63 ~ 7.77 (3H,
m), 7.95 (1H, d, J = 2.2Hz).

1- [1-methyl-1- (7-chloronaphthalen-2-yl) ethyl] -4-methyl-3- (2-
Fluorophenyl) -3-pyrrolin-2-one (Compound No. 15) IRν film cm-1: 1656. NMR (270MHz, CDCl ₃ ) δppm: 1.94 (6H,
s), 2.17 (3H, s), 4.00 (2H, s), 7.05 ~ 7.17 (2H, m), 7.28 ~ 7.
54 (4H, m), 7.68 ~ 7.84 (4H, m).

Reference Example 1 N- [1-methyl-1- (4-chloronaphthalene-2-
Synthesis of (yl) ethyl] -N- (2-oxopropyl) amine In 20 ml of N, N-dimethylformamide, N- [1-
Methyl-1- (4-chloronaphthalen-2-yl) ethyl] amine (1.5 g), potassium carbonate (1.4 g), and chloroacetone (1.3 g) were added, and the mixture was stirred at 80 ° C. for 2 hours. The insoluble matter 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 1.0 g of the desired aminoketone. IRν film cm ^-1 : 3326,1721 NMR (270MHz, CDCl ₃ ) δppm: 1.
75 (6H, s), 2.04 (3H, s), 3.31 (2H, s), 7.50 ~ 7.84 (5H, m), 8.
20 ~ 8.23 (1H, m).

Reference Example 2 N- [1-methyl-1- (4-chloronaphthalene-2-
Synthesis of yl) ethyl] amine Dissolve 4.8 g of sodium hydroxide in 80 ml of water and
4.2 g of bromine was added dropwise with stirring. After returning to room temperature and stirring for 1 hour, the mixture was cooled to 0 ° C again and stirred for 2 or 2 hours.
-Dimethyl-2- (4-chloronaphthalen-2-yl)
6.0 g of acetamide was added at once. After stirring at the same temperature for 1 hour, the temperature was raised to 80 ° C. and stirring was continued for 1 hour. The reaction mixture was extracted with ethyl acetate, dried over anhydrous sodium sulfate, and ethyl acetate was distilled off under reduced pressure to obtain 3.8 g of the desired amine. IRν film cm ^-1 : 3345 .NMR (270MHz, C
DCl ₃ ) δppm: 1.78 (6H, s), 7.51〜7.85 (5H, m), 8.19〜8.24
(1H, m).

Reference Example 3 2,2-Dimethyl-2- (4-chloronaphthalene-2-)
Synthesis of (yl) acetamide In 50 ml of 85% sulfuric acid, 2,2-dimethyl-2- (4-
Chloronaphthalen-2-yl) acetonitrile 6.0 g
Was added and stirred at 80 ° C. for 30 minutes. The reaction mixture was poured into ice water, extracted with ethyl acetate, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 6.5 g of the desired amide. IRν film cm ^-1 : 3344,1666 NMR (270MHz, CDCl ₃ ) δppm: 1.
77 (6H, s), 5.20 ~ 5.40 (2H, broad s), 7.47 ~ 7.91 (5H, m),
8.18 ~ 8.29 (1H, m).

Reference Example 4 2,2-Dimethyl-2- (4-chloronaphthalene-2-)
Il) Synthesis of acetonitrile To 25 ml of N, N-dimethylformamide, 2.7 g of sodium hydride was added, and the mixture was stirred at 0 to 5 ° C.
6.0 g of (4-chloronaphthalen-2-yl) acetonitrile was added. After stirring at the same temperature for 1 hour, 9.7 g of methyl iodide was added, and the mixture was further stirred at 5 ° C to room temperature for 1 hour. The reaction mixture was poured into ice water, extracted with ethyl acetate, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 6.6 g of the target compound. IRν film cm ^-1 : 2237 NMR (270MHz, CDCl ₃ ) δppm: 1.81 (6
H, s), 7.58 ~ 7.64 (3H, m), 7.86 ~ 7.89 (2H, m), 8.23 ~ 8.26
(1H, m).

Reference Example 5 Synthesis of 2- (4-chloronaphthalen-2-yl) acetonitrile To 80 ml of water, 6.2 g of potassium cyanide was added, and 8.1 g of 2-bromomethyl-4-chloronaphthalene with stirring at room temperature. Dichloromethane solution (80 ml) and tetranormal butyl ammonium sulfate 1.1 g were added. After stirring at room temperature for 4 hours, the reaction mixture was extracted with dichloromethane and dried over anhydrous sodium sulfate. After the solvent was distilled off under reduced pressure, silica gel column chromatography was carried out to obtain 6.0 g of the target compound. IRν film cm ^-1 : 2264 .NMR (270MHz, CDCl ₃ ) δppm: 3.89 (2
H, s), 7.50 (1H, d, J = 1.5Hz), 7.56 ~ 7.66 (2H, m), 7.76 (1H,
s), 7.83 to 7.87 (1H, m), 8.24 to 8.27 (1H, m).

Reference Example 6 Synthesis of 2-bromomethyl-4-chloronaphthalene To 170 ml of carbon tetrachloride, 11.3 g of 4-chloro-2-methylnaphthalene was added, and further 11.5 g of N-bromosuccinimide and a catalytic amount. Benzoyl peroxide of
Heat to reflux temperature. After stirring for 30 minutes at the reflux temperature, the mixture was poured into ice water, extracted with dichloromethane, and dried over anhydrous sodium sulfate. After the solvent was distilled off under reduced pressure, silica gel column chromatography was performed to obtain 8.1 g of the target compound. NMR (270 MHz, CDCl ₃ ) δppm: 4.61 (2H, s), 7.55 to 7.62 (3H,
m), 7.75 (1H, s), 7.80 to 7.83 (1H, m), 8.24 (1H, d, J = 8.1Hz)
.

[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; polyoxyethylene nonyl phenyl ether): 1
Parts by weight, white carbon: 5 parts by weight and diatomaceous earth 72
The weight part was pulverized and mixed well to obtain a wettable powder.

[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:
77 parts by weight were pulverized and mixed well to obtain a wettable powder.

Formulation Example 3 (Wettable powder) Compound (4) 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
The wettable powder was obtained by pulverizing and mixing using an et-O-mizer.

[Formulation Example 4] (Powder) Compound (8) of the present invention: 1 part by weight, Emulgen 910 (trade name, manufactured by Kao; polyoxyethylene nonylphenyl ether): 0.5 part by weight and kaolin clay: 98. 5
The parts by weight were pulverized and mixed well to obtain a powder.

[Formulation Example 5] (Powder) Compound (6) 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 ground. Then, a powder was obtained.

Formulation Example 6 (Granule) Compound (12) 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 ligninsulfonate): 2 parts by weight, 72.7 parts by weight of bentonite and 23 parts by weight of talc were mixed well, and then an appropriate amount of water was added to wet the mixture. And extruded 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 7] (Granule) Compound (5) of the present invention: 0.5 part by weight, Gohsenol (G
osenol) GL-05s (PV from Nippon Gohsei)
A): 2 parts by weight, sun extract P252) Sanyo Kokusaku Pulp made sodium benzene sulfonate): 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 8 (Emulsion) Compound (4) of the present invention: 10 parts by weight, Solpol 800A
An emulsion was obtained by mixing and dissolving 10 parts by weight (trade name, manufactured by Toho Chemical: a mixture of a nonionic surfactant and an anionic surfactant) and 80 parts by weight of o-xylene.

[Formulation Example 9] (Flowable agent) Compound (4) of the present invention: 5 parts by weight, sodium ligninsulfonate: 2 parts by weight, xanthan gum: 0.3 part by weight, and polyoxyethylene alkylaryl ether: 1 part by weight Then, 91.7 parts by weight of water was added and mixed, and then finely pulverized using a sand grinder to obtain a flowable agent.

[Formulation Example 10] (Dry flowable agent) Finely pulverized compound (11) of the present invention: 60 parts by weight, alkylbenzenebenzenesulfonate sodium: 5 parts by weight and polypropylene glycol polyethylene glycol ether:
35 parts by weight were mixed to obtain a dry flowable agent. [Test Example 1] Flooded soil treatment (pre-emergence treatment) 1/500000 hectares Wagner pots were filled with soil, water was admixed, and oysters were sewn, and then sea bream, firefly,
Seeds of eels and azaleas were sown to establish a submerged state. Two rice seedlings (2 to 3 leaf stage) that had been raised in advance were used as one strain, and the two strains were transplanted and grown in a greenhouse. One day later (before the emergence of weeds), a prescribed amount of the test compound was treated with a wettable powder prepared according to the method described in Formulation Example 1 above. The submersion depth was kept at 3 cm, and from the day after the treatment, 1 cm of water leakage per day was given for 10 days by a method in which the water in the pot was dripped out from the bottom of the pot by a glass tube. Process 30
After a day, we observed and investigated the occurrence of weeds and the damage to rice plants. The results are shown in Table 1 (Tables 1 to 3). In the table, the degree of damage to the test plant and the degree of phytotoxicity to paddy rice are indicated by the following criteria in comparison with the air-dry weight in the case of no treatment. Growth rate (%) shown by air dry weight ratio to the untreated plot 100 0 to 5 9 6 to 10 8 11 to 20 7 21 to 30 6 31 to 40 5 41 to 60 4 61 to 70 3 71 to 80 2 81 ~ 90 1 91 to 95 0 96 to 100 In addition, the comparative compounds A and B represent the following compounds.
(Same for Test Example 2) A: 1- [1-methyl-1- (3-chlorophenyl) ethyl] -4-methyl-3-phenyl-3-pyrroline-2
-One B: 1- [1-methyl-1- (3,5-dichlorophenyl) ethyl] -4-methyl-3- (2-fluorophenyl) -3-pyrrolin-2-one (Comparative compounds A and B are , A compound described in JP-A-3-204855.) C: 1- [1-methyl-1- (benzothiazole-2-
Iyl) ethyl] -4-methyl-3-phenyl-3-pyrrolin-2-one (Comparative compound C is the compound described in JP-A-6-25160).

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[Table 1]

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[Table 2]

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[Table 3] In the present test, the herbicide according to the present invention showed a high herbicidal effect against the paddy field weeds tested in the low-dose treatment, and showed excellent safety against paddy rice. Comparative compounds A, B, and C showed phytotoxicity to paddy rice at doses that completely killed weeds.

[Test Example 2] Flooded soil treatment (growth season treatment) 1/500000 hectares Wagner pots were filled with soil, watered and scavenged, and then sea bream, firefly,
Seeds of eels and azaleas were sown to establish a submerged state. Two rice seedlings (2 to 3 leaf stage) that had been raised in advance were used as one strain, and the two strains were transplanted and grown in a greenhouse. When the leaf-latch was in the 2 leaf stage, it was treated with a wettable powder prepared by adjusting a predetermined amount of the test compound according to the method described in the above Preparation Example 2. Keep the submersion depth at 3 cm, and from the day after the treatment,
A method of allowing water in the pot to drip out from the bottom of the pot with a glass tube was supplied with 1 cm of water leakage per day for 10 days.
Thirty days after the treatment, the occurrence of weeds and the chemical damage to paddy rice were observed and investigated. The results are shown in Table 2 (Tables 4-6).
It was shown to. In the table, the degree of damage to the test plant and the degree of chemical damage to paddy rice are shown in the same manner as in Test Example 1.

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[Table 4]

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[Table 5]

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[Table 6] In this test, the herbicide according to the present invention showed a high herbicidal effect against the paddy field weeds tested, and showed excellent safety against paddy rice even in the case of low-dose treatment. Comparative compounds A, B, and C showed phytotoxicity to paddy rice at the doses for killing weeds.

[Test Example 3] Chemical damage test according to depth of rice planting 1/50000 hectare Wagner pots were filled with soil, and water was admitted and puddled. Two rice seedlings (2 to 3 leaf stage) that had been raised in advance are used as one strain, and the transplantation depth is 1c.
Two strains each were transplanted at m and 2 cm and grown in a greenhouse. One day later, a prescribed amount of the test compound was added to the above-mentioned Preparation Example 2
Treatment was performed using a wettable powder prepared according to the method described in 1. The submerged depth was kept at 3 cm, and the plant was then grown in a greenhouse. Thirty days after the treatment, the phytotoxicity of paddy rice was observed and investigated. The results are shown in Table 3 (Tables 7 to 9). In the table,
The degree of phytotoxicity to paddy rice was displayed as in Test Example 1.

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[Table 7]

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[Table 8]

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[Table 9] In this test, the herbicide according to the present invention showed excellent safety even for paddy rice planted with 1 cm. Comparative compound A,
B and C showed strong phytotoxicity even for the low-dose treatment to the paddy rice planted with 1 cm.

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INDUSTRIAL APPLICABILITY The 3-pyrrolin-2-one derivative represented by the general formula (I) according to the present invention is a novel compound, and herbicides containing the compound of the present invention are various weeds which cause problems in paddy fields. On the other hand, it shows herbicidal activity at a low dose from pre-emergence to post-emergence growth. In addition, it shows excellent selectivity to rice, and it shows stable selectivity to leaked rice fields and shallowly planted rice, so it can be used safely.

Front page continued (72) Inventor Shingo Matsuo 1144, Togo, Mobara-shi, Chiba Mitsui Toatsu Chemical Co., Ltd. ) Inventor Tomoko Mitsuhashi 1144 Togo, Mobara-shi, Chiba Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Shungo Fukai 1144, Togo, Mobara-shi, Chiba Mitsui Toatsu Chemical Co., Ltd.

Claims (2)

[Claims] 1. A compound of the general formula (I) (In the formula, X represents a hydrogen atom or a fluorine atom, Y represents a halogen atom, and n represents 1 or 2.) A 3-pyrrolin-2-one derivative represented by the formula. 2. The general formula (I) (Chemical Formula 2) (Wherein, X represents a hydrogen atom or a fluorine atom, Y represents a halogen atom, and n represents 1 or 2), and a 3-pyrrolin-2-one derivative represented by the formula is contained. Herbicide.