JPH05221809A - Herbicidal composition for paddy field - Google Patents

Abstract

PURPOSE:To obtain a herbicide for paddy fields showing synergistic effects with a small amount of active ingredients used, usable any period before emergence of weeds and rice transplantation to growth by combining a specific new pyrrolidinone derivative with a diphenyl ether derivative. CONSTITUTION:A herbicide for paddy fields comprising a new 3,4-trans-4- ethyl-3-(substituted phenyl)-1-(3-isopropylphenyl)-2-pyrrolidinone derivative [e.g. 3,4-trans-4-ethyl-3-(3-chlorophenyl)-1-(3-isopropylphenyl)-2-pyrrolidi none] of formula I (X is F, Cl or Br substituted at the 3-position or F substituted at the 3-position and the 4-position or at the 3-position and the 5-position) and at least one of 2,4,6-trichlorophenyl 4-nitrophenyl ether, methyl 5-(2,4-dichlorophenoxy)-2- nitrobenzoate and 2,4-dichlorophenyl 3-methoxy-4-nitrophenyl ether as active ingredients. The compound of formula I is obtained from a compound of formula II (Y is halogen).

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention makes use of novel 3,4-trans-4-ethyl-3- (substituted phenyl) -1- (3-isopropylphenyl) -2-pyrrolidinone derivatives and diphenylether derivatives. The present invention relates to a herbicide composition for paddy fields, which is contained as an ingredient.

[0002]

2. Description of the Related Art Conventionally, various compounds and admixtures have been known as herbicides for paddy fields. Furthermore, recently, a mixture which is called a one-shot treatment agent and which can control various weeds by one treatment has been developed. However, these herbicides require relatively large amounts of active ingredients, and although they are called one-shot treatment agents, they cannot control important weeds accurately by one treatment, and the duration of their effects is short. There are not a few cases that have. Therefore, with a smaller amount of active ingredient,
Development of paddy field herbicides that can control important weeds accurately and for a long time is desired.

[0003]

DISCLOSURE OF THE INVENTION The present invention uses a smaller amount of active ingredient and can be used at any time from the occurrence of weeds before rice planting to the growing season, and the important weeds of paddy fields can be treated by one treatment. An object is to provide a herbicide for paddy fields that can be controlled for a long period of time.

[0004]

Means and Actions for Solving the Problems The inventors of the present invention have conducted extensive studies on a mixture of pyrrolidinone derivatives to solve the above problems, and as a result, by mixing the pyrrolidinone derivative and the diphenyl ether derivative, they were separated individually. A herbicide for paddy fields that shows unexpected synergistic effects from effects and can be used at any time from before weeding before rice planting to the growing season by using less active ingredients and can control important weeds in paddy fields for a long period of time. The present invention has been completed by finding that the above can be obtained.

That is, the present invention has the general formula (I)

[0006]

[Chemical 2] (In the formula, X represents a fluorine atom substituted at the 3-position, a chlorine atom, a bromine atom, a fluorine atom substituted at the 3-position and 4-position, or a 3-position and the 5-position). , 4-trans-4-ethyl-3- (substituted phenyl) -1- (3
-Isopropylphenyl) -2-pyrrolidinone derivative, 2,4,6-trichlorophenyl 4-nitrophenyl ether (hereinafter referred to as compound A), methyl 5- (2,4-dichlorophenoxy)
2-nitrobenzoate (hereinafter referred to as compound B) or at least one of 2,4-dichlorophenyl 3-methoxy-4-nitrophenyl ether (hereinafter referred to as compound C) as an active ingredient A herbicide composition for paddy field.

Of the compounds included in the composition of the present invention,
The compound group represented by the general formula (I) is a novel compound,
It is produced by the method represented by the reaction formula (1) (chemical formula 3).

[0008]

[Chemical 3] That is, in the general formula (II) (in the formula, X is a fluorine atom substituted at the 3-position, a chlorine atom, a bromine atom, a fluorine atom substituted at the 3-position and 4-position or a 3-position and 5-position). Can be easily produced by cyclizing an amide derivative represented by Y is a halogen atom.).
Examples of the cyclizing agent effective for this cyclization reaction include trialkyltin hydride represented by tributyltin hydride, and the reaction is generally carried out in an aromatic solvent such as benzene, toluene and xylene. .. Reaction temperature is 50 ~
The temperature is 140 ° C, preferably 80 to 120 ° C. Also,
The reaction proceeds by adding a radical generator such as a catalytic amount of α, α-azobisisobutyronitrile or benzoyl peroxide to the reaction solution. Irradiating with light is also an effective means. Further, after the completion of the reaction, a method of treating with an appropriate alkali is also effective in order to obtain the desired 3,4-trans isomer in good yield.

The compounds A, B and C according to the present invention are all known compounds, and are described in Japanese Patent No. 529947, respectively.
Japanese Patent No. 4804309, Japanese Patent No. 4820294, etc. Further, Compound A has a general name of chlornitro-phen, Compound B has a general name of bifenox, and Compound C has a general name of chloro. It is commercially available as methoxynil and is put to practical use.

The compound group represented by the general formula (I) has excellent activity as a herbicide for paddy fields, and is highly active especially for the millet, the eel, the annual broad-leaved leaves, etc. Low. On the other hand, compounds A, B, C
Is effective against many weeds such as millet, eel, and firefly, but its use is very inferior when used in low doses, and there is a problem in that the duration of the effect is particularly short.

As described above, the compounds represented by the general formula (I) and the compounds A, B and C may not be expected to have sufficiently satisfactory herbicidal effects when used alone, and in particular, the compounds A, B and C may not be expected. Cannot be expected to be highly effective when used at low doses.

Then, the present inventors examined the mixed use of the compound of the general formula (I) and the compounds A, B and C, and showed a synergistic effect which could not be expected at first, and as a result, each of them alone We have found a herbicidal composition capable of controlling important weeds in paddy fields accurately and for a long period of time without using harm to the paddy rice, by using far less active ingredients than the use.

The thus-obtained herbicidal composition according to the present invention is generally mixed with an inert liquid carrier or solid, and is a commonly used formulation form such as powders, granules, wettable powders, emulsions and flowables. 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,
Examples thereof include mineral powders such as calcium carbonate, diatomaceous earth, and white carbon, vegetable powders such as soybean powder and starch, polymer compounds such as petroleum resin, polyvinyl alcohol, 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 auxiliaries, surfactants, binders, stabilizers and the like usually used in agricultural and horticultural chemicals can be used alone or in combination as required. 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 ethylene oxide or propylene oxide to alkylphenol, higher alcohol, alkylnaphthol, higher fatty acid, fatty acid ester and the like are preferable. As anionic ones, alkylphenols,
Alkyl naphthols, higher alcohols, higher fatty acids, fatty acid esters and the like are preferably alkyl sulfonates, alkyl sulfate ester salts, phosphoric acid ester salts and the like. Further, lignin sulfonate and the like are also preferable examples.

An excellent herbicidal effect can be expected in a wide range of the mixing ratio of the pyrrolidinone derivative represented by the general formula (I), which is a component contained in the herbicidal composition according to the present invention, and the compounds A, B and C. .. However, the mixing ratio of both is usually 0.1 to 1000 parts by weight of each of the compounds A, B and C to 1 part by weight of the pyrrolidinone derivative, preferably 1 to 1 part by weight of the pyrrolidinone derivative to each of the compounds A, B and C. 1
It is 00 parts by weight.

Although the herbicidal composition according to the present invention is effective in various treatment methods, it is preferably used in the treatment of flooded soil. The application rate is 0.01 Kg to 50 K for the mixture
Although it can be used in a wide range of g / ha, it is preferably used in a range of 0.1 to 10 Kg / ha as a standard.

The herbicidal composition according to the present invention may be used in combination with one or more other herbicides, or with agrochemicals such as fungicides, insecticides and plant growth regulators, fertilizers, soil conditioners and the like. Not only this is possible, but 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 pyrrolidinone derivative according to the present invention will be explained with reference to examples. Example 1 3,4-trans-4-ethyl-3- (3-
Chlorophenyl) -1- (3-isopropylphenyl)
Synthesis of 2-pyrrolidinone [Compound No.-4] N- (2-butenyl) -N- (3
-Isopropylphenyl) -2-chloro-2- (3-chlorophenyl) acetamide (1.5 g) was added, and while stirring at reflux temperature, 1.2 g of tributyltin hydride and α,
A small amount of α-azobisisobutyronitrile (AIBN) was added. Continue stirring for 10 minutes, then return to room temperature and DBU
0.3 ml was added and the mixture was further stirred for 5 minutes. The reaction solution was concentrated with an evaporator and column chromatography was performed to obtain 0.9 g of the target compound.

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

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

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

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

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

3,4-trans-4-ethyl-3- (3
-Bromophenyl) -1- (3-isopropylphenyl) -2-pyrrolidinone [Compound No.-5] IRνnujol cm ^-1 : 1700 NMR (CDCl ₃ ) δPPM: 0.97 (3H, t, J = 7.6Hz), 1.21 ( 6H, d, J =
6.6Hz), 1.52 ~ 1.59 (1H, m), 1.71 ~ 1.76 (1H, m), 2.38 ~
2.50 (1H, m), 2.89 ~ 2.94 (1H, m), 3.45 (1H, d, J = 10.3Hz),
3.57 (1H, dd, J = 8.8Hz, 9.5Hz), 4.00 (1H, dd, J = 8.1Hz, 8.8H
z), 7.04 (1H, d, J = 7.3Hz), 7.15〜7.43 (6H, m), 7.64 (1H, s) mp 82.0〜83.2 ℃

Formulation Examples and Test Examples Next, formulation examples and herbicidal activity test examples of the herbicide according to the present invention will be shown.

Formulation Example 1 (wettable powder) Compound (1): 5 parts by weight, Compound (A): 45 parts by weight,
Neoperex (trade name, manufactured by Kao; sodium dodecylbenzenesulfonate): 2 parts by weight, Neugen EA80
(Product name, manufactured by Sanyo Kasei; polyoxyethylene nonylphenyl ether): 2 parts by weight, white carbon: 5 parts by weight and 41 parts by weight of diatomaceous earth were well pulverized and mixed to obtain a wettable powder.

Formulation Example 2 (Flowable Agent) Compound (2): 2 parts by weight, Compound (B): 10 parts by weight,
Sun extract P-252 (trade name, manufactured by Sanyo Kokusaku Pulp; sodium lignin sulfonate): 3 parts by weight and water: 8
4.6 parts by weight were wet pulverized with a sand mill, and further Kerzan S (trade name, manufactured by Kerco; xanthan gum): 0.2
Parts by weight and Deltop (trade name, manufactured by Takeda Pharmaceutical Co., Ltd .; organic iodine-based fungicide): 0.2 parts by weight were added to obtain a flowable agent.

Formulation Example 3 (powder) Compound (3): 1 part by weight, Compound (C): 20 parts by weight,
Emulgen 910 (trade name, manufactured by Kao; polyoxyethylene nonylphenyl ether): 0.5 parts by weight, kaolin clay: 75.5 parts by weight, and white carbon: 3 parts by weight were well pulverized and mixed to obtain a powder. ..

Formulation Example 4 (Granule) Compound (4): 1 part by weight, Compound (A): 7 parts by weight, Gosenol GL-05S (PVA manufactured by Nippon Synthetic Chemical Industry): 2 parts by weight, Sun Extract P252 (Brand name, manufactured by Sanyo Kokusaku Pulp; sodium lignin sulfonate): 2 parts by weight and clay: 88 parts by weight were well mixed, then an appropriate amount of water was added to wet them, and then extrusion granulation was carried out by an injection molding machine. .. This was air-dried at 60 to 90 ° C. and crushed, and then sized to 0.5 to 2 mm with a sizing machine to obtain a granule.

Formulation Example 5 (Emulsion) Compound (5): 1 part by weight, Compound (B): 10 parts by weight,
Emulsion was obtained by mixing and dissolving 10 parts by weight of Solpol 800A (trade name, manufactured by Toho Kagaku; a mixture of a nonionic surfactant and an anionic surfactant) and 79 parts by weight of o-xylene.

Test Example 1 Submerged Soil Treatment (Pre-Emergence Treatment) The soil was filled in a 1/5000 arengren pot, and seeds of Tainubie, firefly, eel, and annual broad-leaved seeds were sown to make 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 predetermined amount of the test composition was treated with granules prepared according to the method described in Formulation Example 4 above, and after 30 days, the occurrence situation of weeds and phytotoxicity to paddy rice. I investigated the situation. The results are shown in Table 1 (Tables 1 to 5). 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 air dry weight in the case of no treatment.

[0034] Growth rate (%) 50 to 5 (withered) 4 6 to 10 (severe damage) 3 11 to 40 (intermediate damage) 2 41 to 70 (small damage) 1 71 ~ 90 (Slight harm) 0 91 ~ 100 (Harmless)

[0035]

[Table 1]

[0036]

[Table 2]

[0037]

[Table 3]

[0038]

[Table 4]

[0039]

[Table 5]

As shown in the results of this test, the herbicidal composition according to the present invention can accurately control important weeds in paddy fields without damaging the paddy fields. Furthermore, their herbicidal effects show superior synergistic effects as compared with the use of each alone, which makes it possible to extend the herbicidal spectrum and use at lower doses.

Test Example 2 Flooded Soil Treatment (Growth Stage Treatment) The soil was filled in a 1/5000 arengren pot and seeds of Tainubie and firefly were sowed to make it a flooded state. Add 2 seedlings (2 to 3 leaf stage) that have been raised in advance to this.
The two strains were transplanted and grown in a greenhouse. When the leaf was one leaf, a predetermined amount of the test composition was treated with a flowable agent prepared according to the method described in Formulation Example 2, and after 30 days, the occurrence of weeds and phytotoxicity to paddy rice. I investigated the situation. The results are shown in Table 2 (Tables 6 to 11). In the table, the degree of damage to the test plant and the degree of phytotoxicity to paddy rice are shown in the same manner as in Test Example 1. Also,
In order to further clarify the synergistic effect due to the mixing, the expected effect at each mixing was calculated by the following method and described together with the measured value. If the measured value of the effect by the test exceeds the calculated value, it can be judged that there is a synergistic effect.

Calculation Formula Used for Predicting Effect (5-Level Evaluation) X: Effect when Herbicide i is Used in αKg / ha Y: Effect when Herbicide ii is Used in βKg / ha E: Herbicide i αKg / ha, herbicide ii βKg / h
a Expected effect when used E = X + Y-XY / 5 (SRColby., "Calculating Synerigistic and Antagon
istic Responsesof Herbicide Combinations "Weeds 1
5,20-22 (1973))

[0043]

[Table 6]

[0044]

[Table 7]

[0045]

[Table 8]

[0046]

[Table 9]

[0047]

[Table 10]

[0048]

[Table 11]

As can be seen from the results of this test, the herbicidal composition according to the present invention can accurately control important weeds in paddy fields without damaging them even during the growing season of weeds. Furthermore, the herbicidal effect exceeds the predicted value, clearly showing that excellent synergistic action is exhibited, and it is possible to use it at a lower dose.

Test Example 3 Flooded soil treatment (duration of effect) Soil was filled in a 1/5000 arewagner pot to be in a flooded state, and a predetermined amount of a test composition was prepared according to the method described in Formulation Example 4 above. It processed using the adjusted granule. After processing 4
On the 0th day, seeds of Taenia cinerea were sown, and 20 days later, the growth status was investigated. The results are shown in Table 3 (Tables 12 to 1).
4). In the table, the degree of damage to the test plant is shown as in Test Example 1.

[0051]

[Table 12]

[0052]

[Table 13]

[0053]

[Table 14]

As can be seen from the results of this test, the herbicidal composition according to the present invention can control important weeds in paddy fields for a long period of time. The herbicidal effect shows superior synergistic effect as compared with the use of each alone, and it is possible to maintain the effect for a long time with a lower dose.

[0055]

The herbicidal composition according to the present invention comprises a pyrrolidinone derivative represented by the general formula (I) and compounds A and B,
Compared to the herbicidal effect that can be expected when each of C is used alone, the synergistic effect is extremely high, and therefore, it has a high effect on important weeds in paddy fields for a long period with a lower dose. As a result, the herbicidal composition according to the present invention can control important weeds in paddy fields accurately for a long time with a single treatment, has high applicability as a herbicide for paddy fields, and the present invention provides a very useful herbicide. To do.

Front page continued (72) Inventor Daisuke Kishi 1144 Togo, Mogo-shi, Chiba Prefecture Mitsui Toatsu Chemical Co., Ltd. ) Inventor Yoshinobu Shimura 1144, Togo, Mobara-shi, Chiba Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] 1. General formula (I) (Chemical formula 1) (In the formula, X represents a fluorine atom substituted in the 3-position, a chlorine atom, a bromine atom, a 3-position and a 4-position, or a fluorine atom substituted in the 3-position and a 5-position). 3,4-trans-4-ethyl-3- (substituted phenyl) -1- (3-
At least one or more of isopropylphenyl) -2-pyrrolidinone derivatives, 2,4,6-trichlorophenyl 4-nitrophenyl ether, methyl 5- (2,4
-Dichlorophenoxy) -2-nitrobenzoate or 2,4-dichlorophenyl 3-methoxy-4-nitrophenyl ether is contained as an active ingredient in at least one kind of herbicide composition for paddy fields.