JPH07291926A - 4-ethyl-3-pyrrolin-2-one derivative and herbicide containing the derivative - Google Patents

Abstract

PURPOSE:To provide a novel 4-ethyl-3-pyrrolin-2-one derivative extremely excellent as a herbicide, free from phytotoxicity to rice which is a useful crop and stably keeping the effect and phytotoxicity, etc., independently of external factors such as water-leakage. CONSTITUTION:This 4-ethyl-3-pyrrolin-2-one derivative is expressed by the formula I (X is H or F), e.g. 1-[1-methyl-1-(3,5-dichlorophenyl]-4-ethyl-3-(2- fluorophenyl)-3-pyrrolin-2-one. The compound of the formula I can be produced by treating an amide derivative of the formula II with a proper base and subjecting to intramolecular aldol condensation reaction. The starting amide derivative of the formula II is produced by reacting an aminoketone derivative of the formula III with a carboxylic acid derivative of the formula IV in the presence of a base. The aminoketone derivative is produced by reacting 1-[1- methyl-1-(3,5-dichlorophenyl)-1-amino]ethane with a 1-halogeno-2-butanone.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a novel 4-ethyl-3-
The present invention relates to a pyrrolin-2-one derivative and herbicides containing these as active ingredients.

[0002]

2. Description of the Related Art Japanese Unexamined Patent Publication (Kokai) No. 3-204855 discloses a cyclic amide derivative represented by the following general formula (Formula 2) as a herbicide.

[0003]

[Chemical 2] (In the formula, X represents a hydrogen atom or a chlorine atom.) These pyrroline compounds have extremely high activity when used in paddy fields and show a wide range of weeding spectra, but some external factors such as, for example, If water moves downward due to water leakage, etc., it will cause serious chemical damage to paddy rice, which makes it difficult to use it in actual fields.

[0004]

In recent years, there has been a strong demand for a highly selective herbicide that does not harm crops and kills only weeds. Further, in paddy fields, effective herbicides that can reliably control difficult-to-control weeds such as millet, firefly, eel, and cypress 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 are soil quality of paddy fields, weather conditions such as temperature and light, inundation depth, water leakage, water movement due to inflow and outflow, and sometimes differences in rice planting depth. Are singly or intricately intertwined,
The effect of a drug on weeds, phytotoxicity on crops, or stability of the effect greatly varies. One of the most important of these variables is the effect of water leakage. In many leaky fields, water,
In addition, the use of herbicides must be significantly restricted due to the occurrence of phytotoxicity due to the downward movement of the drug or the fluctuation of the effect.

Therefore, the present invention does not harm rice in the paddy field, has a wide range of weeding spectrum with a low dosage, and can be used for a wide period from before the emergence of weeds to the growing season after emergence, Another object of the present invention is to provide a selective herbicide that does not show changes in effects and phytotoxicity due to external factors such as water leakage.

[0007]

Means and Actions for Solving the Problems The inventors of the present invention have conducted research on 3-pyrroline derivatives in order to solve the above-mentioned problems, and as a result, have not disclosed the above-mentioned prior art specifically, 4-ethyl -3-pyrrolin-2-one derivative
It is extremely excellent as a herbicide, and it does not cause damage to rice, which is a useful crop, and is also affected by external factors such as water leakage.
It has been found that it has excellent characteristics such as no change in effect and drug damage. That is, the present invention provides the compound represented by the general formula (I)

[0008]

[Chemical 3] (In the formula, X represents a hydrogen atom or a fluorine atom.) A 4-ethyl-3-pyrrolin-2-one derivative represented by the formula, and a herbicide containing the same.
The 4-ethyl-3-pyrrolin-2-one derivative of the present invention is a novel compound and is produced by the method represented by the reaction formula (1) (chemical formula 4).

[0009]

[Chemical 4] That is, it is produced by treating an amide derivative represented by the general formula (II) (wherein X represents a hydrogen atom or a fluorine atom) with a suitable base to promote an intramolecular aldol condensation reaction. be able to.

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, methanol,
Examples thereof include lower alcohols such as ethanol, propanol and butanol, and aprotic solvents such as dimethylformamide and dimethylacetamide. The reaction temperature is −
The 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
It is produced by the method represented by the reaction formula (2).

[0012]

[Chemical 5] That is, the aminoketone derivative represented by the general formula (III) and the carboxylic acid derivative represented by the general formula (IV) (wherein X represents the same meaning as described above and Q represents a halogen atom) are suitable. It is produced by reacting in the presence of various bases. 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, ethyl acetate. And esters such as butyl acetate. Suitable bases are triethylamine, pyridine, dimethylaniline, diisobutylethylamine, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, etc., and the reaction proceeds at any temperature.

The aminoketone derivative of the general formula (III) is produced by reacting 1- [1-methyl-1- (3,5-dichlorophenyl) -1-amino] ethane with 1-halogeno-2-butanone. The carboxylic acid derivative represented by the general formula (IV) is a commercial product. Where 1
-A method for producing halogeno-2-butanone will be described. 1
Specific compounds of -halogeno-2-butanone are 1-bromo-2-butanone and 1-chloro-2-butanone. The 1-halogeno-2-butanone used in the present invention can be produced by photoreaction of 1,2-butylene oxide with bromine or chlorine. The amount of bromine or chlorine used in the present invention is 1 mol of 1,2-butylene oxide,
It is 0.7 mol to 2.0 mol, preferably 0.8 mol to 1.2 mol. The reaction solvent is a mixed solvent of water and an organic solvent such as n-hexane, petroleum ether, benzene, toluene and xylene. The mixing ratio of water and the organic solvent is water: organic solvent = 1: 0.01 to 1: 100, preferably 1: 1 to 1:20. Also, an alkali can be added as a reaction aid. The alkali to be added is sodium hydrogen carbonate, sodium carbonate, sodium hydroxide, potassium hydrogen carbonate, potassium carbonate, potassium hydroxide or the like, and preferably sodium hydrogen carbonate or potassium hydrogen carbonate. The amount of the reaction aid to be added is 0.7 mol to 2.0 mol, preferably 0.8 mol to 1.2 mol, per 1 mol of 1,2-butylene oxide. The reaction temperature is 0 ° C to the reflux temperature of the reaction solvent, preferably 10 ° C to 30 ° C. The reaction time varies depending on the temperature, but is usually 10 minutes to 100 hours. The light source is preferably a visible light lamp. An extraction method is preferable as a method for obtaining a reaction product from the reaction solution obtained by the above method. The extraction solvent used is n-hexane, petroleum ether, ethyl acetate, methyl ethyl ketone, diethyl ether, chloroform,
Methylene chloride, carbon tetrachloride, benzene, toluene, xylene, n-butyl alcohol and the like are preferable, and the solvent used in the reaction is preferable. Further, as a method of removing water from the extract, anhydrous sodium sulfate and anhydrous magnesium sulfate are desirable.

The herbicide containing the compound of the present invention thus obtained as an active ingredient has, as its action characteristics, harmful weeds which cause problems 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 is not harmful to rice, which is 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,
It can be used effectively.

The presence of an ethyl group at the 4-position of the pyrroline ring 3
-Pyrroline derivatives are described in the above-mentioned prior art (JP-A-3-204
855), 1- [1-methyl-1- (3
Although only -chlorophenyl) ethyl] -4-ethyl-3-phenyl-3-pyrrolin-2-one is disclosed,
The compound of the present application has an ethyl group at the 4-position of the pyrroline ring, and 1-methyl-1- (3,3 at the 1-position of the pyrroline ring.
The feature is that a 5-dichlorophenyl) ethyl group is introduced. In improving the performance as a herbicide, as a result of various studies by the present inventors, introduction of an ethyl group at the 4-position of the pyrroline ring and 1-methyl-1- (3,5-dichlorophenyl) ethyl group at the 1-position of the pyrroline ring When this compound is treated as a herbicide, it is of great significance and, as is clear from the test examples described below, there is almost no phytotoxicity in the presence of water leakage, and fluctuations in its effect are hardly observed. But it can be used safely with high effect. In addition, the shallowly planted rice can be safely used without any chemical damage.

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 granule or hydrate which is a commonly used preparation form. It is used by preparing it as a medicine, emulsion or the like. 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 agents, and is not limited to a particular carrier. For example, as a solid carrier, clay, talc, bentonite, calcium carbonate, diatomaceous earth, mineral powder such as white carbon,
Examples thereof include soybean powder, vegetable powder such as starch, petroleum resin, polymer compounds such as polyvinyl alcohol and polyalkylene glycol, urea, waxes and the like. 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 (for example, lignin sulfonic acid, alginic acid, polyvinyl alcohol, gum arabic, CMC sodium, etc.) usually used for agricultural and horticultural agents, a stabilizer (for example, 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 in combination. 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 general formula (I) in the herbicide according to the present invention varies depending on the formulation form, but is usually 1 to 50% by weight for wettable powder and 0.01 to 10% for granules. %, 0.1 to 50% by weight for emulsions, preferably 10 to 40% by weight for wettable powders, 0.1 to 5% by weight for granules, and 1 to 30% by weight for emulsions. 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 herbicides of the present invention represented by the general formula (I) are 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.

[0021]

EXAMPLES Next, the production method of the compound of the present invention will be specifically explained with reference to examples. Example 1 1- [1-methyl-1- (3,5-dichlorophenyl)
Ethyl] -4-ethyl-3- (2-fluorophenyl)
Production of -3-pyrrolin-2-one [Compound No.-1] N- [1-Methyl-1-] in 30 ml of dichloromethane.
4.5 g of (3,5-dichlorophenyl) ethyl] -N- (2-oxobutyl) amine and 3.9 g of pyridine were added, and 8.5 g of 2-fluorophenylacetic acid chloride was added dropwise at 5 to 10 ° C. After stirring at room temperature for 1 hour, 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 30 ml of ethyl acetate. After adding 10 ml of a 28% methanol solution of sodium methylate and stirring under reflux for 15 minutes, the temperature was returned to room temperature, water was added, and the mixture was extracted with ethyl acetate. It was washed with a 12% aqueous hydrochloric acid solution and a saturated aqueous solution of sodium hydrogen carbonate, and dried over anhydrous sodium sulfate. By concentrating with an evaporator and performing column chromatography, 1- [1-methyl-1- (3,5-dichlorophenyl) ethyl] -4-ethyl-3- (2-fluorophenyl) -3 of the present invention is obtained. 2.5 g of pyrrolin-2-one was obtained. NMR (270 MHz, CDCl ₃ ) δppm: 1.26 (3H, t, J = 7.3Hz), 1.78 (6H,
s), 2.49 (2H, q, J = 7.3Hz), 4.11 (2H, s), 7.12 ~ 7.28 (7H, m).
IRν film cm ^-1 : 1687 In the same manner as in Example 1, 1- [1-methyl-1- (3,5-dichlorophenyl) ethyl] -4 according to the present invention was used.
-Ethyl-3-phenyl-3-pyrrolin-2-one [Compound No.-2] was produced. The physical properties are described below. NMR (270 MHz, CDCl ₃ ) δppm: 1.26 (3H, t, J = 7.3Hz), 1.78 (6H,
s), 2.63 (2H, q, J = 7.3Hz), 4.08 (2H, s), 7.23〜7.42 (8H, m).
IR ν film cm ^-1 : 1682 In addition, a production example of an important intermediate for producing the compound of the general formula (I) of the present invention will be described below as a reference example.

Reference Example 1 Preparation of 1-bromo-2-butanone 200 g of 1,2-butylene oxide and 212 of sodium hydrogen carbonate in 750 ml of n-hexane and 375 ml of water.
g, and 402 g of bromine was added dropwise at 10 ° C to 30 ° C over 2 hours under irradiation of a visible light lamp. Extraction with n-hexane, 993 g of 1-bromo-2-butanone in hexane
Got

Reference Example 2 N- [1-methyl-1- (3,5-dichlorophenyl)
Production of ethyl] -N- (2-oxobutyl) amine In 50 ml of N, N-dimethylformamide, N- [1-
Methyl-1- (3,5-dichlorophenyl) ethyl] amine 6.2 g, triethylamine 7.7 g, and 1-
20.9 g of a hexane solution of bromo-2-butanone was 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 ethyl acetate. After drying over anhydrous sodium sulfate, the mixture was concentrated with an evaporator and subjected to silica gel column chromatography to obtain 4.0 g of the desired aminoketone. IRν film cm ⁻¹ : 3330,1718 n _D 24.6 ° C.:1.4587 Formulation Examples and Test Examples Next, formulation examples and herbicidal activity test examples of the herbicide according to the present invention are 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 syclite:
A wettable powder was obtained by thoroughly pulverizing and mixing 77 parts by weight.

Formulation Example 3 (Wettable powder) Compound (1) 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 (Granule) Compound (2) 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 5 (Granule) Compound (1) of the present invention: 0.5 part by weight, Gohsenol (G
Osenol) GL-05s (PV from Nippon Synthetic Chemical Industry)
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 6 (Emulsion) Compound (2) of the present invention: 10 parts by weight, Solpol 800A
(Trade name, manufactured by Toho Kagaku Co., Ltd .: 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 Example Test Example 1 Flooded soil treatment (pre-emergence treatment) 1/500000 hectares Wagner pots were filled with soil, watered and dewatered, then Tainubie, 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 was given for 10 days by a method in which water in the pot was dripped out from the bottom of the pot through a glass tube. Processing 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 (Table 1). 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. 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, Comparative Compounds A and B represent the following compounds (the same applies to Test Example 2). A: 1- [1-methyl-1- (3,5-dichlorophenyl) ethyl] -4-methyl-3-phenyl-3-pyrrolin-2-one B: 1- [1-methyl-1- (3- Chlorophenyl) ethyl] -4-ethyl-3-phenyl-3-pyrroline-2
-ON (Comparative compounds A and B are compounds described in JP-A-3-204855)

[0031]

[Table 1] 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 and B showed phytotoxicity to paddy rice at the dose that completely killed weeds.

Test Example 2 Submerged Soil Treatment (Growth Stage Treatment) 1/500000 hectares Wagner pots were filled with soil, watered and dewatered, 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 2 to 3).
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.

[0033]

[Table 2]

[0034]

[Table 3] 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 and B 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 (Table 4). In the table, the degree of phytotoxicity to paddy rice is indicated as in Test Example 1.

[0036]

[Table 4] In this test, the herbicide according to the present invention showed excellent safety even for paddy rice planted with 1 cm. Comparative compound A,
And B also showed strong phytotoxicity to 1 cm planted rice even in the low dose treatment.

[0037]

The 4-ethyl-3-pyrrolin-2-one derivative represented by the general formula (I) according to the present invention is a novel compound, and a herbicide containing the compound of the present invention causes problems in paddy fields. It shows herbicidal activity against various weeds 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.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Sadafumi Eda 1144, Togo, Mobara-shi, Chiba Mitsui Toatsu Chemical Co., Ltd.

Claims (2)

[Claims] 1. General formula (I) (Chemical formula 1) (In the formula, X represents a hydrogen atom or a fluorine atom.) A 4-ethyl-3-pyrrolin-2-one derivative represented by the formula. 2. A herbicide containing the 4-ethyl-3-pyrrolin-2-one derivative according to claim 1.