JP2662274B2 - Pyrrolidinone derivative, production method thereof and herbicide containing the same as active ingredient - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a pyrrolidinone derivative, a method for producing the same, and a herbicide containing the compound as an active ingredient.

[Prior Art] It has already been known that pyrrolidinone derivatives have herbicidal activity (JP-A-52-89666).

However, these compounds are not satisfactory both in terms of activity level and selectivity between crops and weeds. For example, when these compounds are used in paddy fields, the phytotoxicity on the rice is enormous and must be regarded as a problem in practical use.

Therefore, there is a strong demand for the development of a drug having a high selectivity for useful crops such as rice and wheat and having a wide range of herbicidal effects from grasses to broadleaf weeds at low doses.

[Problems to be solved by the invention]

An object of the present invention is to provide a selective herbicide which does not cause harm to crops in cultivation of crops and has an effective effect on weeds which are harmful to cultivation of crops at a low dose.

[Means and actions for solving the problem]

The present inventors have studied many compounds with the aim of developing herbicides having high selectivity for useful crops. As a result, the pyrrolidinone derivative according to the present invention has an excellent selective herbicidal action at a low dose and with an extremely wide range of herbicidal effects, without causing harm to useful crops, especially rice and wheat. We have found and completed the present invention.

That is, the present invention provides a compound represented by the general formula (I) [Wherein R represents a group (II-a), (II-b), (II-c) or (II-d) (Where R ² is a hydrogen atom, a halogen atom, a cyano group,
A nitro group, a lower alkyl group, a lower alkoxy group or a trifluoromethyl group, R ³ is a halogen atom, a lower alkyl group or a lower alkoxy group, L is an integer of 0 to 4,
M represents an integer of 0 to 3, and N represents an integer of 0 to 2. ), R ¹ represents a hydrogen atom, a halogen atom or a lower alkyl group, Q represents an oxygen atom or a sulfur atom, X and Y each independently represent a hydrogen atom, a lower alkyl group or a halogen atom, and Z represents Indicates a halogen atom. And a method for producing the same and a herbicide containing them as an active ingredient.

The pyrrolidinone derivative of the present invention is a novel compound represented by the general formula (I).

Herbicides containing the compound of the present invention as an active ingredient include, as its action characteristics, harmful weeds which are problematic, for example, grass weeds such as paddy field weeds, broadleaf weeds such as azena, kikasigusa, mizochobe, and cyperaceae such as fireflies. It is excellent against perennial broadleaf weeds such as weeds and urikawa, and broadleaf weeds such as Aoubiyu, Hotokenosa, Onamomi, Shiroza, Hakobe, Marubaasagao, and Asakusaagao in the field, and grass weeds such as barley, barnyardgrass, enokirogusa, enokorogusa, and oakaku. It has a herbicidal effect.
On the other hand, it does not show phytotoxicity to useful crops such as rice, wheat, and corn.

The pyrrolidinone derivative of the present invention is produced by the following method. That is, the general formula (III) [Wherein R represents a group (II-a), (II-b), (II-c) or (II-d) (Where R ² is a hydrogen atom, a halogen atom, a cyano group,
A nitro group, a lower alkyl group, a lower alkoxy group or a trifluoromethyl group, R ³ is a halogen atom, a lower alkyl group or a lower alkoxy group, L is an integer of 0 to 4,
M represents an integer of 0 to 3, and N represents an integer of 0 to 2. ), R ¹ represents a hydrogen atom, a halogen atom or a lower alkyl group; Q represents an oxygen atom or a sulfur atom; X and Y each independently represent a hydrogen atom, a lower alkyl group or a halogen atom; Indicates a halogen atom. Can be synthesized by heating in a catalyst and an unmodified solvent. The reaction temperature is 50 to 18
At 0 ° C, preferably between 120 and 170 ° C.

Suitable catalysts are transition metal ions such as vanadium,
Copper, molybdenum, ruthenium or silver ions or complexes thereof, such as cuprous chloride / di-n-butylamine, cuprous chloride / piperidine and the like.

Suitable inert solvents include, for example, aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene and dichlorobenzene, acid amides such as dimethylformamide, and diethylene glycol dimethyl ether.

This cyclization gives rise to both possible isomeric forms of the compounds of the general formula (I), both cis- and trans-isomers. Usually, it is obtained as a mixture of isomers, but can be separated into individual isomers by an appropriate method such as silica gel column chromatography, distillation, fractional crystallization and the like. Unless otherwise stated, compounds of the general formula (I) represent a mixture of isomers.

The N-allylacetamide represented by the general formula (III) includes a novel compound, but can be synthesized by an ordinary method.
As an example, (route A) is shown below.

(In the formula, R, R ¹ , Q, X, Y and Z each have the above-mentioned meaning.
A, B and C each represent a halogen atom. As shown in route (A), an allyl halide is reacted with a reaction intermediate (V) obtained by reacting RA in the presence of a base with a substituted aniline (IV) in an inert solvent,
Subsequently, a halogen-substituted acetyl halide is reacted, or a halo-substituted acetyl halide is first reacted, followed by an allyl halide to obtain N-allylacetamide (III).

The reaction temperature is 0 to 200 ° C., respectively, and the reaction time may be long, but usually proceeds for 1 to 10 hours. After completion of the reaction, perform the usual treatment, silica gel column chromatography,
Purification by distillation or the like gives the desired compound (III).

Examples of the inert solvent include aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, and dichlorobenzene; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, and dichloroethane; acetone, methyl ethyl ketone, and methyl isobutyl ketone. And aprotic polar solvents such as dimethylformamide, dimethylsulfoxide, and dimethylimidazolidinone. Examples of the base include inorganic bases such as sodium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, and sodium alcoholate; and organic bases such as triethylamine and pyridine.

The application amount of the pyrrolidinone derivative of the present invention can be used in any amount as necessary to control the growth of weeds, and the amount of the active ingredient is typically in the range of 0.05 to 5 kg per hectare, preferably, It ranges from 0.1 to 0.5 kg per hectare.

The herbicide according to the present invention contains the compound represented by the general formula (I) of the present invention as a main component. The compound represented by the general formula (I) of the present invention may be used as it is for the plant to be treated as it is. But,
Generally, the compound represented by the general formula (I) of the present invention includes
Carriers and other adjuvants are added and mixed as necessary, and a commonly used preparation form, for example, powder, granule, wettable powder, emulsion,
It can be used as a herbicide adjusted to flowable preparations and the like.

Carriers include inorganic substances such as clays, talc, bentonite, calcium carbonate, diatomaceous earth, zeolite, and silicic acid anhydride; organic substances made of plants such as flour, soybean powder, starch, crystalline cellulose, etc .; Polymer compounds such as vinyl and polyalkylene glycol; urea; waxes and the like. Further, liquid carriers such as various oils, organic solvents, water and the like can also be used.

As auxiliary agents, for example, lubricants, dispersants, fixing agents,
Spreading agents and the like can be used alone or in combination as needed.

As the auxiliary agent used for the purpose of wetting, dispersion, spreading, component stabilization, physical property stabilization, etc., various surfactants or high polymers such as gelatin, albumin, sodium alginate, methylcellulose, polyvinyl alcohol, xanthan gum, etc. Compounds or other auxiliaries. In the case of a flowable agent, an industrial bactericide or an antibacterial / fungicidal agent may be added for antibacterial and antifungal purposes.

As the surfactant, a nonionic, anionic, cationic or amphoteric surfactant can be used as appropriate. Preferred examples include alkyl phenols, higher alcohols, alkyl naphthols, higher fatty acids, fatty acid esters, dialkyl phosphate amines polymerized with ethylene oxide and propylene oxide, alkyl sulfate salts (such as sodium lauryl sulfate), and alkyl sulfonates. (Such as sodium 2-ethylhexene sulfonate), aryl sulfonates (sodium lignin sulfonate,
Sodium dodecylbenzenesulfonate).

The content of the compound represented by the general formula (I) in the herbicide according to the present invention varies depending on the form of preparation, but is usually 0.01 to 5% by weight for powder, 1 to 50% by weight for wettable powder, and for granules. 0.1-5% by weight, 1-50% by weight for emulsion,
It is 1 to 50% by weight for the flowable preparation and 1 to 50% by weight for the dry flowable preparation. The content of the adjuvant is 0 to 80% by weight, and the content of the carrier is 100% by weight minus the content of the active ingredient compound and the adjuvant.

The herbicide of the present invention is used by mixing one or more of other herbicides, or by mixing with pesticides such as insecticides, plant growth regulators, etc., and soil improving agents or fertilizers. As a matter of course, it is also possible to prepare a mixed preparation with these, and a synergistic effect can be expected in some cases.

〔Example〕

The method for synthesizing the compound of the present invention will be described with reference to examples.

(Synthesis Example 1) 1-3- (2-chloro-4-trifluoromethylphenoxy) phenyl-3-chloro-4-chloromethyl-2-
Synthesis of pyrrolidinone (Compound No. 1) N-3- (2-chloro-4-trifluoromethylphenoxy) phenyl-N-allyl-dichloroacetamide
1.75 g (4 mmol) was dissolved in 10 ml of toluene, and 0.20 ml of n-dibutylamine and 0.04 g of cuprous chloride were added. The reaction solution was heated to reflux for 8 hours under a stream of nitrogen, allowed to cool, and then the reaction mixture was washed with 1N hydrochloric acid, an aqueous solution of sodium hydrogen carbonate and saturated saline, and extracted with ethyl acetate. After drying and concentrating the organic layer, it was purified by column chromatography to give 83
The oily product was obtained in a% yield.

(Synthesis Example 2) 1-3- (3-chloro-5-trifluoromethyl-2-
Synthesis of pyridyloxy) -phenyl-3-chloro-4-chloromethyl-2-pyrrolidinone (Compound No. 7) N-3- (3-chloro-5-trifluoromethyl-2)
0.88 g (2 mmol) of -pyridyloxy) phenyl-N-allyl-dichloroacetamide are dissolved in 6 ml of xylene,
0.10 ml of n-dibutylamine and 0.02 g of cuprous chloride were added. The reaction solution was heated to reflux for 1 hour under a stream of nitrogen, allowed to cool,
The reaction mixture was washed with 1N-hydrochloric acid, aqueous sodium hydrogen carbonate solution and saturated saline, and extracted with ethyl acetate. The organic layer was dried and concentrated, and then purified by column chromatography to obtain 87%
An oily target product was obtained in a yield of 1.

Table 1 shows the physical property values of the compound synthesized as described above.

In addition, a synthesis example of a compound represented by the general formula (III), which is an intermediate for synthesizing the compound of the general formula (I) of the present invention, is shown below as a reference example.

(Reference Example 1) N-3- (3-chloro-5-trifluoromethyl-2-
Synthesis of pyridyloxy) phenyl-N-allyl-dichloroacetamide 1.6 g (4.9 mmol) of 3- (3-chloro-5-trifluoromethyl-2-pyridyloxy) -N-allylaniline
And triethylamine 1.2 ml dichloromethane solution,
0.51 ml (5.3 mmol) of dichloroacetyl chloride under ice cooling
The mixture was added dropwise and further stirred at room temperature for 1 hour. Then, the reaction mixture was washed with 1N hydrochloric acid, a 10% aqueous sodium hydroxide solution and saturated saline. The organic layer was dried and concentrated, and then purified by column chromatography to obtain an oily target compound at a yield of 93%.

NMR (CCl4)? Ppm; 3.462 to 4.05 (m, 2H), 4.42 to 4.65
(M, 1H), 5.02 ~ 5.58 (m, 2H), 5.65 ~ 6.08 (m, 1H), 6.1
5 to 6.68 (m, 3H), 6.92 to 7.42 (m, 1H), 7.92 to 8.08 (m, 1
H), 8.25 to 8.45 (m, 1H) (Reference Example 2) Synthesis of 3- (3-chloro-5-trifluoromethyl-2-pyridyloxy) -N-allylaniline 1.9 g of 3- (allylamino) phenol 13 mmol) and
To a mixture of 0.85 g (13 mmol) of 85.5% potassium hydroxide in dimethylformamide was added dropwise 3.0 g (14 mmol) of 2,3-dichloro-5-trifluoromethylpyridine at room temperature.
Stirred at C for 3 hours. The reaction mixture was poured into ice water and extracted with ethyl acetate, and then purified by column chromatography to obtain an oily target compound in a yield of 78%.

NMR (CCl4)? Ppm; 4.23 (d, J = 6 Hz, 2H), 5.14-5.36
(M, 2H), 5.56-6.12 (m, 2H), 6.76-7.64 (m, 4H), 8.0
0 to 8.08 (m, 1H), 8.22 to 8.32 (m, 1H) Next, preparation examples and herbicidal activity test examples of the herbicide according to the present invention will be described.

Formulation Example 1 (Wetting agent) Compound (1) of the present invention: 20 parts by weight, sodium alkylbenzenesulfonate: 2 parts by weight, polyoxyethylene alkylphenyl ether: 2 parts by weight, and siegrite: 76 parts by weight are thoroughly pulverized and mixed. To obtain a wettable powder.

Formulation Example 2 (Floable agent) Compound (7) of the present invention: 20 parts by weight, sodium ligninsulfonate: 2 parts by weight, xanthan gum: 0.3 part by weight, polyoxyethylene alkylaryl ether: 1 part by weight, water: 76.7 parts by weight Was added and mixed, and then pulverized using a sand grinder to obtain a flowable agent.

Formulation Example 3 (Dust) A dust is obtained by mixing and grinding 5 parts by weight of the present compound (9), 5 parts by weight of sodium ligninsulfonate, 4 parts by weight of polyoxyethylene alkylaryl ether and 86 parts by weight of clay. Was.

Formulation Example 4 (dry flowable agent) Compound (3) of the present invention: 20 parts by weight, sodium alkylbenzenesulfonate: 5 parts by weight, and polypropylene glycol polyethylene glycol ter: 75 parts by weight were mixed.
It was pulverized using an et-O-miser to obtain a dry flowable agent.

Formulation Example 5 (granules) Finely pulverized compound (12) of the present invention: 0.3 part by weight, Gosenol GL-05s (trade name of Nippon Synthetic Chemical Co., Ltd .;
Polyvinyl alcohol): 2.0 parts by weight, sun extract P-25
2 (trade name of Sanyo Kokusaku Pulp Co., Ltd .; sodium ligninsulfonate): 2.0 parts by weight and 95.7 parts by weight of clay are mixed well, then an appropriate amount of water is added to wet, and then extruded by an injection molding machine. Granulated. This was air-dried at 60 to 90 ° C. and crushed, and then sized with a sizing machine to 0.3 to 1 mm to obtain granules.

Formulation Example 6 (emulsion) Compound (2) of the present invention: 10 parts by weight, Solpol 800A (trade name of Toho Chemical Co., Ltd .: mixture of nonionic surfactant and anionic surfactant): 10 parts by weight and xylene: An emulsion was obtained by mixing and dissolving 80 parts by weight.

Test Example 1 [Field foliage treatment test] A field soil was filled in a 1/10000 ares resin pot, and seeds of morning glory, bluegrass, chickweed, napsuna, barnyardgrass, fly, corngrass, corn, and wheat were sowed one by one, and placed in a greenhouse. To grow. When each plant became 2-3 leaves, each compound was made into a solution with acetone containing polyoxyethylene sorbitan monooleate and sorbitan monolaurate, and a predetermined amount was sprayed using a pressurized micro atomizer. The application rate was 2 kg per hectare. The effects on crops and weeds were observed 21 days after the application of the chemicals. Table 2 shows the results.

In the table, the degree of phytotoxicity to crops and the herbicidal effect on weeds were examined according to the following criteria by comparing the growth state of crops or weeds with the air-dry weight in the case of no treatment.

As a result of this test, the compound of the present invention showed an excellent herbicidal effect on the main weeds in the field, and also showed an excellent selectivity on crop corn and wheat as compared with the control compound.

[Single-flooded soil treatment test before germination of paddy field] Soil was packed in a 1/5000 arewagner pot, and seeds or tubers of foxtail, conger, firefly, and urikawa were sowed and flooded. Two rice seedlings (2 to 3 leaf stage) which had been raised in advance were used as one strain, and the two strains were transplanted and grown in a greenhouse.

One day after transplanting the paddy rice, a predetermined amount of the test compound was treated under flooding using granules prepared according to the method described in Formulation Example 5 before the emergence of weeds. And phytotoxicity to paddy rice.

The results are shown in Table-3.

In the table, the degree of phytotoxicity to paddy rice and the herbicidal effect on weeds were examined on the same basis as in Test Example 1 by comparing the state of occurrence or growth of crops or weeds with the air-dry weight without treatment.

As a result of this test, the compound of the present invention showed an excellent herbicidal effect on the main weeds in the paddy field, and also showed an excellent selectivity for transplanted paddy rice as compared with the control compound.

[Effects of the Invention] The herbicide containing the compound represented by the general formula (I) according to the present invention shows a remarkable herbicidal activity at a low dose in all tested weeds, while it is useful crop. No phytotoxicity was observed for a certain rice or wheat even at a remarkably high dose, showing excellent selectivity, and has performance exceeding that of a comparative drug or other known compounds.

Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C07D 207/273 C07D 207/273 401/12 401/12 403/12 403/12

Claims (3)

(57) [Claims] 1. The compound of the general formula (I) [Wherein R represents a group (II-a), (II-b), (II-c) or (II-d) (Where R ² is a hydrogen atom, a halogen atom, a cyano group,
A nitro group, a lower alkyl group, a lower alkoxy group or a trifluoromethyl group, R ³ is a halogen atom, a lower alkyl group or a lower alkoxy group, L is an integer of 0 to 4,
M represents an integer of 0 to 3, and N represents an integer of 0 to 2. ), R ¹ represents a hydrogen atom, a halogen atom or a lower alkyl group, Q represents an oxygen atom or a sulfur atom, X and Y each independently represent a hydrogen atom, a lower alkyl group or a halogen atom, and Z represents Indicates a halogen atom. And a pyrrolidinone derivative represented by the formula: 2. A compound of the general formula (III) [Wherein R represents a group (II-a), (II-b), (II-c) or (II-d) (Where R ² is a hydrogen atom, a halogen atom, a cyano group,
A nitro group, a lower alkyl group, a lower alkoxy group or a trifluoromethyl group, R ³ is a halogen atom, a lower alkyl group or a lower alkoxy group, L is an integer of 0 to 4,
M represents an integer of 0 to 3, and N represents an integer of 0 to 2. ), R ¹ represents a hydrogen atom, a halogen atom or a lower alkyl group, Q represents an oxygen atom or a sulfur atom, X and Y each independently represent a hydrogen atom, a lower alkyl group or a halogen atom, and Z represents Indicates a halogen atom. N represented by
General formula (I) comprising heating arlacetamide in an inert solvent in the presence of a catalyst (Wherein, R, R ¹ , Q, X, Y, and Z represent the above-mentioned meanings). 3. A compound of the general formula (I) [Wherein R represents a group (II-a), (II-b), (II-c) or (II-d) (Where R ² is a hydrogen atom, a halogen atom, a cyano group,
A nitro group, a lower alkyl group, a lower alkoxy group or a trifluoromethyl group, R ³ is a halogen atom, a lower alkyl group or a lower alkoxy group, L is an integer of 0 to 4,
M represents an integer of 0 to 3, and N represents an integer of 0 to 2. ), R ¹ represents a hydrogen atom, a halogen atom or a lower alkyl group, Q represents an oxygen atom or a sulfur atom, X and Y each independently represent a hydrogen atom, a lower alkyl group or a halogen atom, and Z represents Indicates a halogen atom. ] The herbicide which contains the pyrrolidinone derivative represented by these as an active ingredient.