JPS62167708A - Herbicide composition - Google Patents

Abstract

PURPOSE:The titled composition which has large herbicidal effects and weeding spectrum with a small amount free from phytotoxicity, comprising a 1,4- dihydro-4-oxo-3-pyridinecarboxamide compound and at least one of dinitroaniline compounds as active ingredients. CONSTITUTION:A herbicide composition obtained by blending a 1,4-dihydro-4- oxo-3-pyridinecarboxamide compound shown by formula [R is H, vinyl, phenyl, etc.; R3 is H, halogen, cyano, etc.,; R4 and R5 are H, 1-11C alkyl, lower alkenyl, etc., or R3 and R4 are bonded to form (CH2)m (m is 3 or 4); R6 and R7 are halogen or lower alkyl; R8 is substituent group on benzene ring and H, halogen, etc.,] or its addition salt with a dinitroaniline compound shown by formula II (R1 and R2 are H, etc.,; R2 is H or amino; R3 is methyl, trifluoromethyl, etc.,) in a weight ratio of preferably 1:0.1-10.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention provides at least one of (i) a 4-dihydro-4-oxo-3-pyridine carboxamide compound and an addition salt thereof;
The present invention relates to a herbicidal composition containing, as an active ingredient, at least one type of compound belonging to the dinitroaniline derivative group.

PRIOR ART A small number of compounds belonging to the 1,4-dihydro-4-oxo-3-pyridinecarboxamides can be found in the literature. Tetsu Kato, Pharmaceutical Journal, 101 Yu, 40 (
(1981) on the reactivity of ketene derivatives, and Canadian Patent No. 1,115,278 (and J.B.

Pierce et al. J, Med, Chem, 2
5, 131 (1982)) about 4-pyridone compounds having anti-inflammatory effects, and JP-A-54-24
892 further includes JP-A-52-144676 and JP-A-57-1145 as partial structures of cephalosporins.
73 are respectively disclosed as plant growth regulators, especially chemical hybridization agents, but 1 as represented by formula (I)
, 4-dihydro-4-oxo-3-pyridinecarboxamide compound as an active ingredient is not described 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 written document mentioning its unique herbicidal effect.

(Problem to be solved by the invention) To date, many herbicides for upland fields have been developed and used, but they still lack the ability to increase herbicidal effects, expand the herbicidal spectrum, reduce chemical damage, and provide economical effects. There is a strong need for new herbicides that can provide promising results.

In the present invention, the compound represented by formula (I) has a wide herbicidal spectrum against grasses, Cyperaceae, and broad-leaved weeds, and has little phytotoxicity on many broad-leaved crops, including grasses. It has the advantage of having a long residual effect, but it has the disadvantage that it is less effective against well-grown wild plants.

On the other hand, the compound represented by formula (II) is generally highly effective against grass weeds, and is highly safe against many broad-leaved crops such as soybean and cotton, as well as corn, but is not effective against broad-leaved weeds. It has the disadvantage of being low.

The present invention was developed in view of the above problems, and in particular, by blending two types of herbicides each having different herbicidal effects and using fJf', each herbicide has a ii! , due to extremely significant synergistic effects that cannot be expected with independent use,
The purpose is to increase the herbicidal effect, expand the herbicidal spectrum, and reduce the amount used, thereby reducing chemical damage and achieving economic effects.

(Means for Solving the Problems) The present inventors have proposed the formula (I
) and the compound represented by formula (II) in an appropriate ratio, the drawbacks of each being used alone can be compensated for, and due to the extremely remarkable synergistic effect,
The herbicidal spectrum has been greatly expanded, resulting in a high herbicidal effect on a wide variety of crops, from grassy weeds to broad-leaved weeds, with a single spraying in a small amount over the entire growing period. We have discovered excellent features such as chemical damage and have completed the present invention.

The present invention contains at least one compound represented by the following formula (1) and its addition salt, and at least one dinitroaniline compound represented by formula (II) as a TI effective acid component. The present invention relates to a herbicidal composition having f and 'j characteristics.

R In the formula, R is a hydrogen atom, a vinyl group, a phenyl group unsubstituted or substituted with one or two substituents such as a halogen atom, lower alkyl, or lower alkoxy, -〇-R1 (R1 is an alkyl group or an aralkyl group) ), or -(CH2)n-R2
(n is an integer of 1 to 4: R2 is a hydrogen atom, a halogen atom,
Hydroxy group, lower alkoxy group, lower alkoxyalkyl group, mercapto group, lower alkylthio group, amine group, di-lower alkylamino group, c, -C1l alkyl group, lower alkenyl group, lower alkynyl group, cycloalkyl group, 5 or a 6-membered heterocyclic group, or an unsubstituted or) aryl group or arylthio group substituted with 1 or 2 substituents of lower alkyl and lower alkoxy); R3 is a hydrogen atom, a halogen atom, cyano group,
A lower alkyl group, carboxyl group, aryl group, aralkyl group, alkoxycarbonyl group or N-arylcarbamoyl group, R4 and R5 are the same or different and hydrogen atom, C1-C11 alkyl group, lower alkenyl group, lower alkynyl group , a cycloalkyl group, a halogenated lower alkyl group, a lower alkoxyalkyl group, a 5- or 6-membered heterocyclic group, or 4i11. An aryl group or aralkyl group whose nucleus is substituted with one or two substituents of halogen atom, lower alkyl, and lower alkoxy, or R3 and R4 together are -(CH2)m- (m is 3 or 4 ), R6 and R7 are the same or different and each means a halogen atom or a lower alkyl group, and R8 is a substituent on the benzene ring and means a hydrogen atom, a halogen atom or a lower alkyl group, respectively.

In the formula, R and R1 are the same or different and represent a hydrogen atom or a lower alkyl group, R2 represents a hydrogen atom, an amine group or a methyl group, and R3 represents a methyl group, a trifluoromethyl group or R4
-5o2- (R4 is a methyl group or an amine group).

That is, when the compound represented by formula (I) and the dinitroaniline compound represented by formula (II) are used in combination, it is possible to remove broad leaves such as purslane, white grass, and barnyard grass, which are less effective when using the dinitroaniline compound alone. It exhibits a highly synergistic effect against weeds, and can greatly expand its herbicidal spectrum from grassy weeds to broad-leaved weeds. In addition,
The safety of the dinitroaniline compound represented by formula (II) for cotton and soybean is not compromised, and a single application from before to after emergence of 1'16 grass can be applied over the entire growing period of the crop. A high weeding effect can be expected through this method.

Among the active ingredients of the herbicidal composition of the present invention, the compound represented by formula (I) is a new substance and can be produced, for example, by the method shown in the following production example.

Production Example (Method A) (III) [In formula (III), R, R5, R6, R7 and R8 are
Same as the definition of formula (I) 1 This method uses a 3-aminoacrylic acid anilide derivative (I
II) and 2.2.6-)dimethyl-4H-1,3-dioxin-4-one in a suitable solvent (e.g. toluene, xylene, etc.) under heating (e.g. about 100°C to 140°C).
C). Here, 2,
2.6-) dimethyl-4H-1,3-dioxin-4-
2-ethyl-2゜6-dimethyl-4H instead of
It is also possible to use -1,3-dioxin-4-one. In addition, in performing this method, it is not necessary to use an isolated substance for the 3-aminoacrylic acid anilide derivative (III), and the formula R-NH2 (IV) and the formula [formula (IV) and (V)] Medium, R, R5, R5, R7 and R
8 is the same as the definition of formula (I)] It may be used directly as a mixture with. In practice, it is more convenient to use this reaction mixture.

(Method B) [In formulas (VI) and (IV), R, R3, R4, R5, R
(3, R7 and R8 are the same as defined in formula (I) 1 This method is used to prepare a 4-pyrone compound (V
r), that is, 4-oxo-N-phenyl-4H-pyran-3-carboxamide and ammonia or amine or its salt represented by formula (IV) in a suitable solvent (e.g., ethanol, water, etc.) at room temperature. The reaction is carried out at a temperature of ~60°Cfi. The amount of ammonia or amine used is at least equimolar to the 4-pyrone compound, and if necessary, a large excess amount is used. When the amine is obtained as a salt, it is necessary to subject the amine to the reaction in free form with a neutralizing amount or more of an organic or inorganic base.

(Method C) [In formulas (■) and (■), R, R3, R4, R5, R6,
R7 and R8 are the same as defined in formula (I) 1 This method involves combining a carboxylic acid corresponding to formula (I), namely a 1,4-dihydro-4-oxo-3-pyridinecarboxylic acid derivative (■) with aniline The derivative (■) is reacted with the derivative (■) in the presence of a dehydration condensation agent. When carrying out this method, the method using a 1-substituted-2-halopyridinium salt and a tertiary amine as a dehydration condensation agent can be advantageously used, for example, as described in JP-A-52-57102.

(Method D) [In formula (IX) and (■), R, R3, R4, R5, R6
. An acid halide (IX), which can be easily obtained by reacting an aniline monomer (
(2) is reacted with the 1;1R group in the presence of the 1;1R group.

(Method E) Formula (X) [wherein R, R4, R5, R6, R7 and R8
C. A 1,4-dihydro-4-oxo-3-pyridinecarboxamide derivative represented by 1 as defined in formula (I) is reacted with a genating agent, so that R3 in formula (I) is 1
It is possible to produce compounds that have zero gen atoms.

N-chlorosuccinimide or N-chlorosuccinimide is particularly convenient.
- Using a chlorogenating agent such as bromosuccinimide, in a solvent such as a chlorinated hydrocarbon such as dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, tetrachloroethane, etc., with or without a radical initiator. The reaction is carried out in Alternatively, the compound represented by formula (X) is dissolved in the above-mentioned chlorinated hydrocarbon, and the reaction is carried out by blowing chlorine or bromine into the reaction mixture in a gaseous state or dropping it dropwise in a liquid state by an appropriate method. You can also do it.

In the method of halogenating the compound represented by formula (X) as described above, however, a halogen atom may be additionally introduced into the phenyl group on the amide nitrogen.

(Method F) In this method, by treating a compound in which R3 in formula (I) is a halogen atom with an alkali metal halide,
This is an exchange reaction of the halogen atom represented by R3 in formula (I). This method is useful for synthesizing a compound in which R3 in formula (I), 71, is a fluorine atom, which is difficult to introduce directly.

(Method G) This method is carried out by treating a compound in which R3 in formula (I) is a halogen atom with an alkali metal cyanide. is useful for the synthesis of compounds in which R3 is a cyan group.

(Method H) t7 (III) [Formula (III), (X I ), (X II), (
X III), R, R3, R4, R5, R6.

R7 and R8 are the same as defined in formula (I). In this method,
The 3-aminoacrylic acid anilide derivative (III) and the acid chloride (XI) are reacted in the presence of a base to form (XI
I) is obtained and treated with an N,N-dimethylamide dimethyl ketal derivative (XIII). When R4 is a hydrogen atom, instead of N,N-dimethylamide dimethyl ketal derivative (Xllll),
It is also possible to use formic acid esters. This method is
This is effective when R3 is an aryl group.

Examples of the compound represented by formula (I) (hereinafter referred to as compound A) obtained by the above method are shown in Table 1 (hereinafter, specific examples of compound A are compound No. in Table 1). show.).

Further, the compound represented by formula (II) (hereinafter referred to as compound B) is a known substance and can be produced by a known method. Examples of compound B are shown in Table 2 (hereinafter, specific examples of compound *B are indicated by compound No. in Table 2).

The unique herbicidal effect related to the present invention is observed in a fairly wide range of mixing ratios, but when compound A and compound B are mixed at a weight ratio of 10, 1 to 10 (more preferably 1:0.5 to 5). It is preferable to mix them so that In the herbicidal composition of the present invention, the active ingredient compounds of Compound A and Compound B may be used as they are, but generally they are mixed with a solid carrier, a liquid carrier, a surfactant, and other formulation auxiliaries. hydrating agent,
Formulated into granules, near-L formulations, etc.

These preparations contain the herbicide composition of the present invention as the total of the active ingredients of Compound A and Compound B, and in the case of wettable powders, 1
0-80%, 2-20% for granules, 10-5 for IL agents
It is preferable that the content is 0% (all percentages are by weight).

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

Surfactants used for dispersion, monomerization, etc. include polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene Examples include nonionic surfactants such as polyoxypropylene block polymers, anionic surfactants such as alkyl sulfate salts, alkyl sulfonate salts, alkylaryl sulfonate salts, and polyoxyethylene alkyl sulfate salts.

Formulation adjuvants include lignin sulfonates, alginates, polyacrylates, polyvinyl alcohol, vegetable gums, carboxymethyl cellulose (CMC), hydroxyethyl cellulose (HEC), and the like.

(Example) Next, formulation examples are shown. However, the formulation examples of the present invention are not limited to these. In addition, the section indicates the critical danger section.

Formulation Example 1 Wettable powder Compound No. A-1720 parts, Compound No. B-320
part, 40 parts of talc, 15 parts of bentonite, Tsurupol-
2 parts of 9047 (manufactured by Toho Chemical) and 3 parts of Tsurupol 5039 (same as above) were thoroughly ground and mixed to obtain a wettable powder.

Formulation Example 2 fL agent Compound No., A-2115 parts, Compound No., B-215
1 part, 20 parts of xylene, 42 parts of dimethylformamide, and 8 parts of polyoxyethylene alkylphenyl ether were mixed to obtain an fL agent.

The hydrating agent and fL agent prepared as described above are usually diluted with water and used by spraying on soil, mixing with soil, or spraying on foliage.

Furthermore, the herbicide composition of the present invention may be used in combination with other insecticides, acaricides, nematicides, fungicides, herbicides, plant growth regulators, fertilizers, or soil conditioners as necessary. You can also do it. In addition, it is useful not only for fields but also for paddy rice, vegetables, orchards, pastures, lawns, forests, and non-agricultural lands.

Next, the usefulness of the herbicide composition of the present invention will be shown in Examples.

Example: Herbicidal effect and phytotoxicity test 23 A plastic case measuring 26 cm x 26 cm and 3 cm deep was filled with field soil, and weed seeds (e.g.
The soil was sown with seeds (cotton) and crop seeds (cotton) and covered with soil to a depth of 1 to 2 cm. The herbicidal composition of the present invention, made into a wettable powder according to Formulation Example 1, was diluted with a predetermined amount of water and uniformly sprayed onto the soil surface using a small sprayer in a predetermined amount. After spraying, the plants were grown in a greenhouse for 20 days, and their herbicidal effects and phytotoxicity were evaluated according to the criteria below. The results are shown in Tables 3 and 4.

Claims (1)

[Claims] Formula (I): ▲ Numerical formulas, chemical formulas, tables, etc. Phenyl group substituted with a substituent, -O-R_1(R_1
is an alkyl group or an aralkyl group), or -(CH_2)
_n-R_2 (n is an integer from 1 to 4; R_2 is a hydrogen atom,
Halogen atom, hydroxy group, lower alkoxy group, lower alkoxyalkyl group, mercapto group, lower alkylthio group, amino group, di-lower alkylamino group, C_5-C
_1_1 alkyl group, lower alkenyl group, lower alkynyl group, cycloalkyl group, 5- or 6-membered heterocyclic group, or unsubstituted or substituted with 1 to 2 substituents of halogen atom, lower alkyl, and lower alkoxy aryl group and arylthio group); R_3 is a hydrogen atom, a halogen atom, a cyano group, a lower alkyl group, a carboxyl group,
Aryl group, aralkyl group, alkoxycarbonyl group or N-arylcarbamoyl group, R_4 and R_5 are the same or different and hydrogen atom, C_1-C_1_1 alkyl group, lower alkenyl group, lower alkynyl group, cycloalkyl group, lower halogenated group Alkyl group, lower alkoxyalkyl group, 5- or 6-membered heterocyclic group, or aryl group or aralkyl group which is unsubstituted or whose nucleus is substituted with 1 or 2 substituents of halogen atom, lower alkyl or lower alkoxy. , or R_3 and R_4 together -(
CH_2)_m- (m is 3 or 4), R_6 and R_
7 is the same or different and each means a halogen atom or a lower alkyl group, R_8 is a substituent on the benzene ring,
It means a hydrogen atom, a halogen atom, or a lower alkyl group, respectively. ] At least one type of 1,4-dihydro-4-oxo-3-pyridinecarboxamide compound and its addition salt, and the formula (II): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R and R_1 are the same or different and represent a hydrogen atom or a lower alkyl group, R_2 is a hydrogen atom, an amino group or a methyl group, R_3 is a methyl group, a trifluoromethyl group, or R_4-SO_2- (R_4 is a methyl group or an amino group ) respectively. ] A herbicidal composition comprising at least one type of dinitroaniline compound represented by the following as an active ingredient.