JPH0655645B2 - Herbicide composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to at least one of 1,4-dihydro-4-oxo-3-pyridinecarboxamide compounds and addition salts thereof, and at least compounds belonging to pyrazole derivatives. 1
The present invention relates to a herbicidal composition, characterized in that the herbicide composition contains as an active ingredient.

(Prior Art) Conventionally, a small number of compounds belonging to 1,4-dihydro-4-oxo-3-pyridinecarboxamide can be found in the literature. Kato Tetsuzo et al., Pharmaceutical Journal, 101 , 40 (1981), on the reactivity of ketene derivatives, and Canadian Patent No. 1,115,278.
No. 4 (and J. P. Berce et al., J. Med. Chem. 25 , 131 (1982)) describes 4-pyridone compounds having an anti-inflammatory effect, and JP-A-54-24892 discloses a partial structure of cephalosporins. Further, JP-A-52-144676 and JP-A-57-1145
73 is disclosed for plant growth regulators, particularly for chemical mating agents, but relates to herbicides containing a 1,4-dihydro-4-oxo-3-pyridinecarboxamide compound such as Compound A as an active ingredient. Is not listed at all. Furthermore, the herbicidal composition shown in the present invention is a novel combination that has not been described in any literature, and of course, there is no literature that mentions its unique herbicidal effect.

(Problems to be Solved by the Invention) In the present invention, Compound A is highly effective against grass weeds, particularly Taenia edulis, and is also highly effective against Cyperaceae weeds, and has little phytotoxicity to paddy rice. It has a wide suitable period and a long residual effect, but it has the drawback of being less effective against broad-leaved weeds.

On the other hand, Compound B is highly effective against annual broad-leaved weeds and perennial weeds mainly from Urikawa, but has a low effect on grass weeds mainly from Tainubie, which has advanced in growth, and has a short use period width. Have.

The present invention has been made in view of such problems, and in particular, by combining and combining two kinds of herbicides each having a different herbicidal action, a very significant synergistic effect which cannot be expected by each single use, the herbicidal action By increasing the effect, broadening the herbicidal spectrum, and eventually reducing the amount used, the aim is to reduce phytotoxicity and achieve an economic effect.

(Means for Solving the Problems) The present inventors supplemented the drawbacks of individual use by mixing and using the compound A and the compound B having the above-mentioned drawbacks in appropriate proportions, respectively, and was extremely remarkable. The synergistic action significantly expands the herbicidal spectrum and the suitable period for use, and as a result, the entire growing period of paddy rice is achieved with a small amount of a single spray from the annual weeds to the perennial weeds from the early growth stage to the growing season. The present inventors have completed the present invention by finding excellent features such as a high herbicidal effect and no chemical damage to paddy rice.

The present invention includes at least one compound represented by the following formula (I) and its addition salt (compound A), and a compound represented by the following formula (I
It relates to a herbicidal composition comprising at least one compound represented by I) (compound B) as an active ingredient.

In the formula, R is a hydrogen atom, a vinylinyl group, a phenyl group which is unsubstituted or substituted with 1 to 2 substituents such as a halogen atom, lower alkyl and lower alkoxy, -O-R ₁ (R ₁ is an alkyl group or aralkyl group), or _{- (CH 2) n -R 2} (n
Is an integer of 1 to 4; R ₂ is a hydrogen atom, a halogen atom, a hydroxy group, a lower alkoxy group, a lower alkoxyalkyl group, a mercapto group, a lower alkylthio group, an amino group, a di-lower alkylamino group, C ₁ -C ₁₁ Alkyl group, lower alkenyl group, lower alkynyl group, cycloalkyl group,
A 5- or 6-membered heterocyclic group, or an aryl group and an arylthio group which are unsubstituted or substituted with 1 to 2 substituents of a halogen atom, lower alkyl and lower alkoxy);
R ₃ is a hydrogen atom or a lower alkyl group, R ₄ and R ₅ are the same or different and are a hydrogen atom, a C ₁ -C ₁₁ alkyl group,
A lower alkenyl group, a lower alkynyl group, a cycloalkyl group, a halogenated lower alkyl group, a lower alkoxyalkyl group, a 5- or 6-membered heterocyclic group, or an unsubstituted or a nucleus containing a halogen atom, a lower alkyl and a lower alkoxy R ₆ represents an aryl group or aralkyl group substituted with two substituents, and R ₆ is a substituent on the benzene ring, and is a hydrogen atom, a halogen atom, a cyano group, a nitro group, an amino group, a lower alkyl group, a halogen atom. Lower alkyl group,
Hydroxy group, lower alkoxy group, aryloxy group,
It means a carboxy group or a lower alkoxycarbonyl group, respectively.

In the formula, R represents a benzyl group, a phenacyl group or a phenylsulfonyl group in which the benzene ring is unsubstituted or substituted with a methyl group, and R ₁ and R ₂ are the same or different and each represents a hydrogen atom or a methyl group.

Among the active ingredients of the herbicidal composition of the present invention, most of the compounds represented by the formula (I) are novel substances, and they can be produced by, for example, the method shown in the following production examples.

Production example (method A) [Wherein R, R ₅ and R ₆ in the formula (III) are the same as the definition in the formula (I)] This method is carried out using a 3-aminoacrylic acid anilide derivative (II
I) and 2,2,6-trimethyl-4H-1,3-dioxin-4-
ON and a suitable solvent (eg toluene, xylene, etc.)
It is carried out by reacting in medium, with heating (for example, about 100 to 140 ° C.). Where 2,2,6-trimethyl-4H-
Instead of 1,3-dioxin-4-one, 2-ethyl-
It is also possible to use 2,6-dimethyl-4H-1,3-dioxin-4-one. Moreover, in carrying out this method, the 3-aminoacrylic acid anilide derivative (III) is
It is not necessary to use the isolated material and the formula R-NH ₂ (IV) [In the formulas (IV) and (V), R, R ₅ and R ₆ are represented by the formula (I)
Same definition as in the above]. In practice, it is easier to use this reaction mixture.

(Method B) [In the formulas (VI) and (IV), R, R ₃ , R ₄ , R ₅ and R ₆
Is the same as the definition of formula (I)]
I), that is, 4-oxo-N-phenyl-4H-pyran-3-carboxamide and ammonia or amine represented by formula (IV) or a salt thereof in a suitable solvent (eg, ethanol, water, etc.) at room temperature. The reaction is carried out at a temperature of about 60 ° C. The amount of ammonia or ammonium used is equimolar or more to the 4-pyrone compound, and a large excess amount is used if necessary. When the amine is available as a salt,
It is necessary to subject the amine to the reaction in the free form with an organic or inorganic base in a neutralization amount or more.

Examples of compound A obtained by the above method are shown in Table 1 (specific examples of compound A are shown by compound No. in Table 1 below).

In addition, among the active ingredients of the herbicidal composition of the present invention, the formula (I
The compound B represented by I) is a known substance, and examples thereof are shown in Table-2 (hereinafter, specific examples of the compound B are the compounds in Table-2.
It shows with No. ).

The peculiar herbicidal effect according to the present invention is recognized in a considerably wide range of mixing ratios, but the compound A and the compound B are mixed in a weight ratio.
It is preferable to mix them in a ratio of 1: 0.1 to 10 (more preferably 1: 0.5 to 5). In the herbicidal composition of the present invention, the active ingredient compounds represented by the above formulas (I) and (II) may be used as they are, but generally, they are solid carriers, liquid carriers, surfactants and other preparations. Wet powder,
Formulated in granules, emulsions, etc.

In these formulations, the herbicidal composition of the present invention is represented by the above formula (I).
And as the total of the active ingredient compounds represented by the formula (II),
Wettable powder 10-80%, Granules 2-20%, Emulsion 10-10%
It is preferable to contain 50% (both represent% by weight).

Solid carriers used in the preparation include kaolin, bentonite, clays, talc, diatomaceous earth, zealite, zeolite, pyrophyllite, synthetic silicon oxides, calcium carbonate, and other fine powders or granules. Is
Aromatic hydrocarbons such as xylene and methylnaphthalene, alcohols such as ethanol, isopropanol, ethylene glycol and methyl cellosolve, acetone, isophorone, ketones such as cyclohexanone, soybean oil, vegetable oil such as cottonseed oil, dimethylformamide, dimethyl sulfoxide, Examples include acetonitrile and water.

Surfactants used for dispersion, emulsification, etc. include polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene polyoxy. There are nonionic surfactants such as propylene block polymers, anionic surfactants such as alkyl sulfate ester salts, alkyl sulfonates, alkylaryl sulfonates, and polyoxyethylene alkyl sulfate ester salts.

Pharmaceutical auxiliary agents include lignin sulfonate, alginate, polyacrylates, polyvinyl alcohol, plant gums, carboxymethyl cellulose (CMC), hydroxyethyl cellulose (HEC) and the like.

(Example) Next, formulation examples are shown. In addition, a part shows a weight part.

Formulation Example 1 Granules Compound No.A-7 5 parts Compound No.B-1 5 parts, talc 57 parts,
30 parts of bentonite and 3 parts of lignin sulfonate are well pulverized and mixed, water is added and kneaded well, and granulated and dried by an ordinary method to obtain granules.

Formulation Example 2 Granules Compound No.A-57 2 parts, Compound No.B-3 5 parts, talc 60
Parts, bentonite 30 parts, and lignin sulfonate 3 parts are well pulverized and mixed, water is added and well kneaded, and granulated and dried by an ordinary method to obtain granules.

Formulation Example 3 Wettable powder Compound No. A-27 20 parts, Compound No. B-2 20 parts, Talc 40
Part, bentonite 15 parts, Sorpol-9047 (manufactured by Toho Kagaku) 2 parts, and Sorpol 5039 (same as above) 3 parts are well pulverized and mixed to obtain a hydrate.

Formulation Example 4 Emulsion Compound No. A-14 15 parts, Compound No. B-4 15 parts, xylene 20
Parts, 42 parts of dimethylformamide, and 8 parts of polyoxyethylene alkylphenyl ether are mixed well to obtain an emulsion.

The wettable powder and emulsion prepared as described above are usually diluted with water, and the granules are used as they are for soil spraying or foliage / soil spraying.

Further, the herbicidal composition of the present invention can also be used as a mixture with other insecticides acaricides, nematicides, fungicides, herbicides, plant growth regulators, fertilizers or soil conditioners, if necessary. it can.

The herbicidal composition of the present invention is particularly suitable for use in paddy fields. Next, its usefulness is shown in Examples.

Example Herbicidal effect and phytotoxicity test 1 / 5000a Wagner pots were filled with paddy soil, and rice buds, eels, cypress, dogflies, broad-leaved weeds (Azena, Prunus chinensis, Mizojakobe) and pine nut tubers at a depth of 1 to 2 cm. Mixed. After submerging the rice with water to make it into a paddy field, tubers of Urikawa and Mizugaya Tsutsui were planted, and 3.2 leaf stage paddy rice plants were transplanted to 2 strains (2 strains / strain). The water depth was 3 cm.

Three days after the transplanting of paddy rice (the early stage of weed development) and about 10 days after the transplantation (Two leaf stage of Tainubie), a prescribed amount of each of the wettable powders prepared according to Formulation Example 3 was dropped onto the submerged surface.

30 days after the chemical treatment, herbicidal effect and phytotoxicity were evaluated according to the following criteria, and the results are shown in Table-3 and Table-4.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuhisa Masamoto 500 Kamimabe, Himeji City, Hyogo Prefecture (72) Inventor Yoshiyuki Hirako 6-8-2 Kunami, Otake City, Hiroshima Prefecture

Claims (1)

[Claims] 1. Formula (I): [In the formula, R is a hydrogen atom, an unsubstituted phenyl group, a benzyloxy group, or-(CH ₂ ) _n -R ₂ (n is an integer of 1 to 4; R ₂ is a lower alkoxy group C ₁ -C ₁₁ ; An alkyl group,
A cycloalkyl group, a furyl group, a pyridyl group, or a phenyl group which is unsubstituted or substituted with a halogen atom or a lower alkyl group); R ₃ is a hydrogen atom or a lower alkyl group, and R ₄ and R ₅ are the same or different and are C _1- C ₁₁ alkyl group, halogenated lower alkyl group, lower alkoxyalkyl group, furyl group, benzyl group, or unsubstituted or phenyl group whose nucleus is substituted with a halogen atom or a lower alkyl group, and R ₆ Is a substituent on the benzene ring, which means a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkoxycarbonyl group, respectively. ]
A 1,4-dihydro-4-oxo-3-pyridinecarboxamide compound represented by the formula (II) and at least one addition salt thereof (hereinafter referred to as compound A); [In the formula, R represents a benzyl group, a phenacyl group, and a phenylsulfonyl group in which the benzene ring is unsubstituted or substituted with a methyl group, and R ₁ and R ₂ are the same or different and each represents a hydrogen atom or a methyl group. ] At least 1 of the pyrazole type compound represented by these (henceforth compound B).
A herbicidal composition, comprising: