JPH07300456A - New 3-pyrrolin-2-one derivative and herbicide containing the same - Google Patents

Abstract

PURPOSE:To obtain the subject new compound having excellent herbicidal activity, nontoxic to paddy rice, usable over a wide period, excellent in selectivity, thus useful as a herbicide. CONSTITUTION:This compound is expressed by formula I (X is H or F), e.g. 1[1-methyl-1-(naphthalen-2-yl)ethyl]-4-methyl-3-(2-fluorophenyl)3-pyrr olin-2-one. The compound of formula I is obtained by reaction between 1- methyl-1-(naphthalen-2-yl)ethylamine and a halogenoacetone to form a compound of formula II, which is then reacted with a compound of formula III to produce a compound of formula IV, which is, in turn, treated with a base such as an alkali(alkaline earth) metal hydroxide and subjected to intramolecular aldol condensation reaction.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a novel 3-pyrroline-2
-On 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]

[Chemical 3] The compound represented by is disclosed as a herbicide. The pyrroline compound disclosed in JP-A-3-204855 has extremely high activity when used in paddy fields and exhibits 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.

[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 problems, and as a result, they are not disclosed in the above-mentioned JP-A-3-204855. The novel 3-pyrrolin-2-one derivative is extremely excellent as a herbicide and does not cause phytotoxicity to rice, which is a useful crop, and its effects and phytotoxicity are also fluctuated by external factors such as water leakage. It was found that it does not have excellent characteristics. That is, the present invention has the general formula (I)

[0008]

[Chemical 4] (In the formula, X represents a hydrogen atom or a fluorine atom.) A 3-pyrrolin-2-one derivative represented by the formula, and a herbicide containing the same. 3-of the present invention
The pyrrolin-2-one derivative is a novel compound and is produced by the method represented by the reaction formula (1) (formula 5).

[0009]

[Chemical 5] 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 for use 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, metal sodium and metal. Alkali metals such as potassium and lithium metal, metal hydrides such as sodium hydride and lithium hydride, alcoholates such as potassium t-butoxide and sodium alkoxide, picoline, quinoline, 1,8-diazabicyclo [5.4.0]. ] Organic bases, such as undecene-7 (DBU), are mentioned.

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).

[0011]

[Chemical 6] 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-methyl-1- (naphthalen-2-yl) ethylamine with halogenoacetone,
The carboxylic acid derivative represented by the general formula (IV) is a commercial product. The herbicide containing the compound of the present invention thus obtained as an active ingredient has, as its action characteristics, harmful weeds that are problematic in most paddy fields, for example, grass weeds such as Nobye, Cyperaceae, cyperaceae weeds such as firefly, and konjac. It has an excellent herbicidal effect on annual broad-leaved weeds such as Escherichia coli 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 invention compounds of the present application disclose 3-pyrroline derivatives and tetrahydropyridine derivatives in that a 1-methyl-1- (naphthalen-2-yl) ethyl group is present at the 1-position of the pyrroline ring. It is different from the compound described in the above-mentioned prior art (Japanese Patent Laid-Open No. 3-204855). In improving the performance as a herbicide, the presence of the 1-methyl-1- (naphthalen-2-yl) ethyl group at the 1-position of the pyrroline ring is significant, and when the compound of the present invention is treated as a herbicide, the test described below. As is clear from the examples, even if there is a water leak, there is almost no phytotoxicity, and fluctuations in its effect are hardly observed, and it can be safely used with a high effect even in a leaky field. In addition, the phytotoxicity usually seen when paddy rice is planted shallowly is small.

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 solid, and a powder form, a granule form, which is a commonly used formulation form, Used as a wettable powder, 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 agents, and is not limited to a particular carrier. For example, solid carriers include clay, talc, bentonite, calcium carbonate, diatomaceous earth, mineral powders such as white carbon, soybean powder, vegetable powders such as starch, polymers such as petroleum resin, polyvinyl alcohol, polyalkylene glycol and the like. Examples include compounds, urea, waxes and the like. As the liquid carrier, various organic solvents such as xylene, methylnaphthalene, and alkylbenzene,
Examples include various oils such as vegetable oils and water.

As the auxiliary agent, a surfactant, a binder (for example, lignin sulfonic acid, alginic acid, polyvinyl alcohol, gum arabic, CMC sodium, etc.) and a stabilizer (for example, antioxidant, which are usually used in agricultural and horticultural chemicals, are used. 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 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, it is preferable to use alkylphenol, alkylnaphthol, higher alcohol, higher fatty acid, fatty acid ester or the like as an alkyl sulfonate, an alkyl sulfate ester salt, or a phosphate ester salt. 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 is usually 0.01 to 20% by weight for powders and 1 to 50% by weight for wettable powders. , 0.01 to 10% by weight for granules, 0.1 to 50% by weight for emulsions, 0.1 to 50% by weight for flowable formulations, 1 to 5 for dry flowable formulations
0% by weight, preferably 0.1 to 3% by weight for powders, 10 to 40% by weight for wettable powders, 0.1 to 0.1% for granules.
5% by weight, 1-30% by weight for emulsion, 1-30% by weight for flowable formulation, 10-4 for dry flowable formulation
It is 0% by weight. 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 weed 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 used in combination with one or more other herbicides, or pesticides such as fungicides, insecticides and plant growth regulators, fertilizers, soil conditioners, etc. Not to mention that it is possible, a mixed preparation with these is also possible, and in some cases, a synergistic effect can be expected.

[0020]

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- (naphthalen-2-yl) ethyl] -4-methyl-3- (2-fluorophenyl) -3
-Preparation of Pyrrolin-2-one [Compound No.-1] N- [1-Methyl-1-] in 20 ml of dichloromethane
(Naphthalen-2-yl) ethyl] -N- (2-oxopropyl) amine (3.0 g) and pyridine (3.5 g) were added, and 2-fluorophenylacetic acid chloride (1.8 g) 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 20 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. Wash with 6% aqueous hydrochloric acid and saturated aqueous sodium bicarbonate,
It was dried over anhydrous sodium sulfate. By concentrating with an evaporator and performing silica gel column chromatography, 1- [1-methyl-1- (naphthalene-2) of the present invention is obtained.
-Yl) ethyl] -4-methyl-3- (2-fluorophenyl) -3-pyrrolin-2-one (3.7 g) was obtained. mp: 126.0-128.0 ° C IRνKBr (cm ^-1 ): 1667 NMR (270MHz, CDCl ₃ ) δppm: 1.97 (6H, s), 2.00 (3H, s), 3.93
(2H, s), 7.05 to 7.19 (2H, m) 7.26 to 7.34 (1H, m), 7.40 to 7.56 (4H, m), 7.78 to 7.84 (4H, m) In the same manner as in Example 1, 1- [1-methyl-1- (naphthalen-2-yl) ethyl] -4-methyl-3-phenyl-3-pyrrolin-2-one [Compound No.-2] according to the invention was prepared. The physical properties are described below. mp: 122.0-124.0 ° C IRνKBr (cm ^-1 ): 1671 NMR (270MHz, CDCl ₃ ) δppm: 1.97 (6H, s), 2.11 (3H, s), 3.89
(2H, s), 7.26 to 7.60 (8H, m) 7.78 to 7.85 (4H, m) In addition, as an example for synthesizing an important intermediate for synthesizing the compound of the general formula (I) of the present invention, Note.

Reference Example 1 Preparation of N- [1-methyl-1- (naphthalen-2-yl) ethyl] -N- (2-oxopropyl) amine N- [1-] in 20 ml of N, N-dimethylformamide.
Methyl-1- (naphthalen-2-yl) ethyl] amine (4.5 g), potassium carbonate (3.0 g), and chloroacetone (3.8 g) were added, and the mixture was stirred at 80 ° C for 1 hr. 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, concentration with an evaporator and silica gel column chromatography,
5.8 g of the desired aminoketone was obtained. IR ν film (cm ^-1 ): 3326,1720 NMR (270MHz, CDCl ₃ ) δppm: 1.56 (6H, s), 2.02 (3H, s), 3.31
(2H, s), 7.42-7.51 (2H, m) 7.54-7.58 (1H, m), 7.76-7.83 (4H, m) Formulation examples and test examples Formulation examples and herbicidal activity of the herbicide according to the present invention A test example is 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 (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 (Powder) Compound (2) 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
Parts by weight were well pulverized and mixed to obtain a dust.

Formulation Example 5 (Dust) The compound (1) 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 6 (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 7 (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 8 (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.

Formulation Example 8 (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, 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 9 (Dry flowable agent) Finely pulverized compound (2) of the present invention: 60 parts by weight, nalolium alkylbenzenesulfonate: 5 parts by weight and polypropylene glycol polyethylene glycol ether: 3
5 parts by weight were mixed to obtain a dry flowable agent.

Physiological test example Test example 1 Flooded soil treatment (pre-emergence treatment) 1/500000 hectares Wagner pots were filled with soil, watered and dewatered, and 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.

[0033] 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.)

[0034]

[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 Flooded Soil Treatment (Growth Stage Treatment) 1/500000 hectare Wagner pots were filled with soil, watered, and oystered, 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.

[0036]

[Table 2]

[0037]

[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 1/500000 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.

[0039]

[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.

[0040]

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.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Sadafumi Eda 1144 Togo, Mobara-shi, Chiba Prefecture Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Koichi Moriyasu 1144, Togo, Mobara-shi Chiba Prefecture 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 3-pyrrolin-2-one derivative. 2. The general formula (I) (Chemical Formula 2) (In the formula, X represents a hydrogen atom or a fluorine atom.) A 3-pyrrolin-2-one derivative represented by the formula: a herbicide.