JPS62167709A - Herbicide composition - Google Patents

Abstract

PURPOSE:A herbicide composition which has extremely enlarged weeding spectrum and raised herbicidal effects by synergistic action caused by use of both a novel 1,4-dihydro-4-oxo-3-pyridinecarboxyamide compound and a chloroacetamide derivative. CONSTITUTION:A herbicide composition which comprises one or more of a novel compound shown by formula I (R is H, vinyl, phenyl which may contain substituent group such as halogen, etc., OR1, etc.,; R1 is H, 1-11C alkyl, lower alkenyl, lower alkynyl, etc.,; R6-R8 are halogen, lower alkyl and R8 is further H) and its addition salt and one or more of compounds shown by formula II (R is lower alkyl, lower alkoxy or CH2COOR1; R1 is lower alkyl) as active ingredients, compensates for defects of separate use of each components and has high herbicidal effects on weeds from gramineous weeds to broad-leaved weeds with a small amount and by a single application through the whole growth period of various crops free from phytotoxicity to crops.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to at least one type of 1,4-dihydro-4-oxo-3-pyridinecarboxamide compound and its addition salt, and a chloracetamide derivative. Containing at least one type of compound as an active ingredient
．． The present invention relates to a herbicidal composition that has a characteristic of yellowing.

(Prior Art) Until now, a small number of compounds belonging to the 1,4-dihydro-4-oxo-3-pyridinecarboxamide class can be found in the literature. Tetsuzou Kato, Pharmaceutical Journal, 101, 40 (1
981) regarding 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.
No. 73 is disclosed as a plant growth regulator, especially a chemical hybridization agent.
．． There is no mention of herbicides containing 4-dihydro-4-oxo-3-pyridinecarboxamide compounds as active ingredients. Furthermore, the herbicidal composition shown in the present invention is also a novel combination that has not been described in any literature, and of course there is no literature that mentions 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 (1) includes grasses, Cyperaceae weeds, broad-leaved weeds,
It has a wide herbicidal spectrum, has low chemical damage to many broad-leaved crops including grasses, and has a long residual effect, but it has the disadvantage of being less effective against mature grasses. .

On the other hand, the compound represented by formula (II) is generally highly effective against grass weeds, and is highly safe for many broad-leaved crops such as soybean and cotton, as well as grass crops such as corn and rice. Broadleaf '41U grass has the drawback of being less effective.

This introduction was made in view of the above problems,
In particular, by blending and using two types of herbicides, each with a different herbicidal effect, an extremely remarkable synergistic effect that cannot be expected when using each herbicide alone results in eradication.
Increasing the effect, expanding the herbicidal spectrum, and even reducing the amount used! The purpose of this is to reduce the harm caused by drugs, and to have economic and 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, and as a result, from grass weeds to broad-leaved weeds, a single spray can have a high herbicidal effect over the entire growing period of a wide variety of crops. They discovered excellent features such as 4HHF resistance to drug damage and completed the present invention.

The present invention contains as active ingredients at least one compound represented by the following formula (I) and its addition salt, and at least one chloracetamide compound represented by the formula (II) 3:'n The present invention relates to a herbicidal composition having a concentration of '+1M;'t.

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 store, lower alkylthio group, amine group, di-lower alkylamino group, C5-C1l alkyl group, lower alkenyl group, lower alkynyl group, cycloalkyl group, 5 or 6 member heterocyclic group, or unsubstituted or halogen atom, lower alkyl, and lower alkoxy
(aryl group and arylthio group substituted with two substituents); R3 is a hydrogen atom, a halogen atom, a cyan group, a lower alkyl group, a carboxyl group, an aryl group, an aralkyl group, an alkoxycarbonyl group, or an N-arylcarbamoyl group; , R4 and R5 are the same or different hydrogen atoms,
ci-C1l alkyl group, lower alkenyl group, lower alkynyl group, cycloalkyl group, halogenated lower alkyl group, lower alkoxyalkyl group, 5- or 6-membered heterocyclic group, or unsubstituted or whose nucleus is a halogen atom, lower an aryl group or an aralkyl group substituted with one or two alkyl and lower alkoxy substituents, or R3 and R
4 together -(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 is a lower alkyl group, a lower alkoxy group, or -
CH2COO-R1 (R1 is a lower alkyl group).

In other words, when the compound represented by formula (I) and the chloracetamide compound represented by formula (II) are used in combination, the chloracetamide compound alone is less effective against purslane, white grass, barnyard grass, etc. It shows a high synergistic effect against broad-leaved weeds, and can greatly expand the herbicidal spectrum from grass to broad-leaved weeds. In addition, the safety of the chloracetamide compound represented by formula (II) for cotton, soybean, corn, etc. is not impaired, and it can be applied once from before to after emergence of grass. , a high weeding effect can be expected throughout the entire growing period of crops.

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)] This method uses a 3-aminoacrylic acid anilide derivative (I
II) and 2.2.6-)umethyl-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-drimethyl-4H-1,3-dioxin-4-
2-ethyl-26-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 a JJL-separated substance for the 3-aminoacrylic acid anilide 1 transparent conductor (III), and the formula R-NH2 (IV), the formula c, and the formula (IV) ( V) Inside, R, R5, R6, 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, R, 3, R4, R5,
R6, R7 and R8 are the same as defined in formula (I)] This method uses a 4-pyrone compound (V
I), 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'C. 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 Formula 1 (■) and (■), R, R3, R4, R5, R(3
, R7 and R8 are the same as defined in formula (I) 1 The Kono method uses a carboxylic acid corresponding to formula (I), i.e. The aniline derivative (■) is reacted in the presence of a dehydration condensation agent. When carrying out this method, for example, the method described in JP-A No. 52-57102 using a 1-substituted-2-halopyridinium salt and a tertiary amine as a dehydration condensation agent can be advantageously used.

(Method D) [In formula (IX) and (■), R, R3, R4, R5, R(
3, R7 and R8 are the same as defined in formula (I)] This method involves adding a halogenating agent such as thionyl chloride to a 1,4-dihydro-4-oxo-3-pyridinecarboxylic acid derivative (■). 1′ can be easily obtained by reacting
In this method, an acid halide (IX) and an aniline derivative (■) are reacted in the presence of a base.

(Method E) In formula (X) 1, R2R4, R5, R6, R7 and R8
1,t, R3 in formula (I) is reacted with a 1,4-dihydro-4-oxo-3-pyridinecarboxamide derivative represented by 1, which is the same as the definition of formula (I), with a genating agent. It is possible to produce compounds in which is a halogen atom. Flight 091 uses a halogenating agent such as N-chlorosuccinimide or N-bromosuccinimide in a solvent such as a chlorinated hydrocarbon such as dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, or tetrachloroethane. The reaction is carried out in the presence or absence of a radical initiator. 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 of formula (I) in which R3 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 the synthesis of compounds in which R3 in formula (I) 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 where is a cyano group.

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

R7 and R8 are the same as defined in formula (I) 1 This method:
A 3-aminoacrylic acid anilide derivative (Ill) and an 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 - is a hydrogen atom, it is also possible to use a formic acid ester instead of the N,N-dimethylamide dimethyl ketal derivative (XIII). This method uses R
This is effective when 3 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.).

In addition, a compound represented by formula (II) (hereinafter, compound B
That's what it means. ) 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 shown as compound No. in Table-2. )
.

The unique herbicidal effect of the present invention is observed in a fairly wide range of mixing ratios, but the ratio of Compound A to Compound B is 1:0.1 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 ThA 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. It is formulated into wettable powders, granules, single drops, 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, 10-50% for emulsions
% (all indicate weight %).

Solid carriers used in formulations include fine powders or granules such as kaolin, bentonite, clays, talc, diatoms, gicrite, zeolite, pyrophyllite, synthetic silicon oxides, and calcium carbonate; In the carrier,
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, emulsification, etc. include polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene polyoxy Examples include nonionic surfactants such as propylene 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, parts indicate parts by weight.

Formulation Example 1 Wettable powder Compound No. A-8820 parts, Compound No. B-120
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-13515 parts, Compound No., B-21
5 parts, xylene 20 parts, dimethylformamide 42 parts,
Eight parts of polyoxyethylene alkyl phenyl ether are thoroughly mixed to obtain an emulsion.

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 (wildweed, foxtail grass,
crabgrass, purslane, whitewort) and crop seeds (dice)
The seeds were sown and covered with soil to a depth of 1 to 2 cm. The herbicide composition of the present invention made into a wettable powder according to Formulation Example 1 is diluted with a predetermined amount of water,
It was uniformly sprayed on the soil surface using a small sprayer in a predetermined amount. After spraying, the plants were grown in a greenhouse for 20 days, and the herbicidal effect 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 is a lower alkyl group, a lower alkoxy group, or -CH_2COO-R_1 (R_1 is a lower alkyl group)
means. ] A herbicidal composition characterized by containing at least one type of chloroacetamide compound represented by the following as an active ingredient.