JPH07188225A - Cyclic amide derivative and herbicide containing the same compound as the active component - Google Patents

Abstract

PURPOSE:To obtain a new cyclic amide derivative exhibiting a herbicidal effect on various kinds of weeds in a remarkably small amount without damaging useful crops. CONSTITUTION:This compound is expressed by formula I [R<1> is a lower alkyl, a lower alkenyl, a lower alkynyl, an aryl which may be substituted or an aralkyl which may be substituted; R<3> is a five- to six-membered heterocyclic group which may be substituted (with H, a halogen, a lower alkyl, a lower alkoxy, a lower haloalkyl or a lower haloalkoxy) or fused with a benzene ring as necessary; R<4> and R<5> are each a lower alkyl; X 18 O or CH2l, e.g. 6-methyl-3-[ 1-methyl-1-(3-thienyl)ethyl]-5-phenyl-2,3-dihydro-4H-1, 3-oxazin-4-one. In the case of X:O, the compound of formula I can be synthesized by reacting a compound of formula II with a compound of formula III in a suitable solvent or without using a solvent at 90 to 160 deg.C. This compound has a high activity on annual and perennial weeds in a paddy field and broad leaf weeds, cyperaceous weeds and gramineous weeds in an upland field.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel cyclic amide derivative not described in the literature and a herbicide containing the same as an active ingredient.

[0002]

BACKGROUND OF THE INVENTION Certain 4 H -2,3-dihydro-1,3-
Oxazin-4-one derivatives have been described in several publications [eg Tetrahedron Lett., 33 , 2905 (1976), Heterocycle.
s, 17 , 298 (1982), Chem. Pharm. Bull., 35 (5), 1860 (1
987), Chem. Pharm. Bull., 35 (5), 1871 (1987), etc.]. However, the compounds described in these documents differ from the compounds of the present invention in that the 3-position is not substituted with a tertiary alkyl group or a tertiary aralkyl group. Further, no mention is made of the herbicidal activity and plant growth regulating activity of these compounds. Further, in US Pat. No. 5,006,157 and US Pat. No. 5,076,834, 1- (1-methyl-1-phenylethyl) -3-phenyl-1,2,5,6-tetrahydropyridin-2-one derivative However, nothing is known about the herbicidal activity of a compound in which the 1-position is substituted with a tertiary ring substituted with a heterocycle as in the present invention.

[0003]

In recent years, there has been a strong demand for a herbicide having a high effect at a low dose and having the selectivity of killing only weeds without damaging the crops. However, the above-mentioned known compounds have a problem that their effects and selectivity are not always satisfactory. An object of the present invention is to provide a novel cyclic amide derivative having high herbicidal activity and excellent in selectivity, and a herbicide containing the same as an active ingredient.

[0004]

As a result of synthesizing novel cyclic amide derivatives and studying their physiological activities, the present inventors have found that a specific cyclic amide derivative can be used in various ways without damaging useful crops. The inventors have found that they have an extremely low dose of herbicidal activity against weeds and completed the present invention. That is, according to the present invention, the following general formula (I):

[0005]

[Chemical 3]

[In the formula, R ¹ represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, an optionally substituted aryl group or an optionally substituted aralkyl group,
R ² represents a hydrogen atom or a lower alkyl group, R ³ represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkyl group or a lower haloalkoxy group in each case, or a benzene ring. And a 5- or 6-membered heterocyclic group which may be condensed with
⁴ and R ⁵ each independently represent a lower alkyl group, and X represents an oxygen atom or a group CH ₂ ] and a herbicide containing the cyclic amide derivative as an active ingredient. next,
Specific examples of the groups defined in the general formula of the present invention are shown below.

Lower alkyl group ; for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl or n-hexyl group. And straight chain or branched lower alkyl groups having 1 to 6 carbon atoms. Lower alkenyl group ; for example, a lower alkenyl group having 2 to 5 carbon atoms such as vinyl, allyl, 2-methyl-2-propenyl, 2-butenyl, 3-butenyl or 3-methyl-2-butenyl group. it can. Lower alkynyl group ; for example, lower alkynyl group having 1 to 5 carbon atoms such as 2-propynyl, 1-methyl-2-propynyl, 2-butynyl or 3-butynyl group.

An optionally substituted aryl group ; for example, naphthyl, phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-methylphenyl, 3-methylphenyl,
4-methylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl, 2-
(Trifluoromethyl) phenyl, 3- (trifluoromethyl) phenyl, 4- (trifluoromethyl) phenyl, 2,6-difluorophenyl or 2-chloro-6
Examples thereof include an aryl group which may be substituted with a halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a nitro group and the like such as a fluorophenyl group.

Aralkyl group which may be substituted ; for example, benzyl, 2-chlorobenzyl, 3-chlorobenzyl, 4-chlorobenzyl, 2-bromobenzyl, 3-bromobenzyl, 4-bromobenzyl, 2-fluorobenzyl. , 3-fluorobenzyl, 4-fluorobenzyl,
2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2-methoxybenzyl, 3-methoxybenzyl, 4-methoxybenzyl, 2-nitrobenzyl, 3-
Nitrobenzyl, 4-nitrobenzyl, 2- (trifluoromethyl) benzyl, 3- (trifluoromethyl) benzyl, 4- (trifluoromethyl) benzyl, 2,6-
Examples thereof include an aralkyl group which may be substituted with a halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkyl group or a nitro group such as a difluorobenzyl or 2-chloro-6-fluorobenzyl group. Halogen atom : fluorine, chlorine, bromine or iodine.

Lower haloalkyl groups ; for example, chloromethyl, dibromomethyl, trifluoromethyl, 1-chloroethyl, 2-ethyl iodide, 2,2,2-trifluoroethyl or 3-chloropropyl groups, etc. Mention may be made of a lower haloalkyl group in which one or more arbitrary hydrogen atoms of the alkyl group have been replaced by the halogen atom. Lower haloalkoxy group ; lower haloalkoxy containing the lower haloalkyl group as an alkyl moiety, such as fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2-chloroethoxy or 1,1,2,2-tetrafluoroethoxy group A group can be mentioned.

Hydrogen atom, halogen atom, lower alkyl
Group, lower alkoxy group, lower haloalkyl group or lower
Optionally substituted with a haloalkoxy group, or
5- or 6-membered heterocyclic ring which may be condensed with the Nzen ring
Group ; for example, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-chloro-6-pyridyl, 2,6-dichloro-4.
-Pyridyl, 2-chloro-4-trifluoromethyl-6
-Pyridyl, 2-trifluoromethyl-6-pyridyl,
2-thienyl, 3-thienyl, 2-furyl, 3-furyl, 2-pyrimidinyl, 4,6-dimethyl-2-pyrimidinyl, 4,6-dimethoxy-2-pyrimidinyl, 4,6
-Dichloro-2-pyrimidinyl, 4-chloro-6-methoxy-2-pyrimidinyl, pyrazinyl, 2-benzoxazolyl, 2-benzothiazolyl, 4-chloro-2-benzothiazolyl, 5-chloro-2-benzothiazolyl,
6-chloro-2-benzothiazolyl, 1-methyl-2-
Benzimidazolyl, 1-methyl-2-indolyl, 1
-Methyl-3-indolyl, 2-benzofuranyl, 2-
Quinolyl, 4,7-dichloro-2-quinolyl, 2-quinoxalinyl, 6-chloro-2-quinoxalinyl, 2-benzodioxanyl or 2,3-dihydro-3,3-dimethyl-5-benzofuranyl and other hetero groups A cyclic group may be mentioned.

Preferred compounds among the compounds represented by the above general formula (I) are those in which R ¹ is selected from the group consisting of a branched alkyl group such as an isobutyl group or an isopropyl group, or a halogen atom and a lower alkyl group. Represents a phenyl group which may be substituted with one substituent, R ² represents a methyl group or an ethyl group, and R ³ represents 2-chloro-6-
Pyridyl, 2,6-dichloro-4-pyridyl, 2-chloro-4-trifluoromethyl-6-pyridyl, 2-trifluoromethyl-6-pyridyl, 2-benzothiazolyl, 4-chloro-2-benzothiazolyl, 5- Chloro-
Examples thereof include 2-benzothiazolyl, 6-chloro-2-benzothiazolyl, 2-benzofuranyl or 2-quinolyl groups, and R ⁴ and R ⁵ both represent a methyl group. Among these compounds, R ¹ represents a phenyl group which may be substituted with one substituent selected from a halogen atom and a lower alkyl group, R ² represents a methyl group, and R ³ represents 2-benzothiazolyl. , 6-chloro-2-benzothiazolyl or 2-benzofuranyl group, wherein R ⁴ and R ⁵ are both methyl groups are particularly preferable.

Specific examples of the compound represented by the general formula (I) according to the present invention are shown in Table 1 below. The meanings of the abbreviations used in the tables of this specification are shown below. Me: Methyl group Et: Ethyl group iPr: Isopropyl group iBu: Isobutyl group Ph: Phenyl group.

[0014]

[Table 1]

[0015]

[Table 2]

[0016]

[Table 3]

[0017]

[Table 4]

[0018]

[Table 5]

[0019]

[Table 6]

[0020]

[Table 7]

[0021]

[Table 8]

[0022]

[Table 9]

[0023]

[Table 10]

[0024]

[Table 11]

[0025]

[Table 12]

[0026]

[Table 13]

[0027]

[Table 14]

[0028]

[Table 15]

[0029]

[Table 16]

[0030]

[Table 17]

[0031]

[Table 18]

[0032]

[Table 19]

[0033]

[Table 20]

[0034]

[Table 21]

[0035]

[Table 22]

[0036]

[Table 23]

[0037]

[Table 24]

[0038]

[Table 25]

[0039]

[Table 26]

The compound represented by the general formula (I) of the present invention may be obtained by any method, for example, it can be produced by the following method. (1) Production of the compound (I ′) of the present invention in which X is an oxygen atom
Method The reaction formula of this production method is shown below.

[0041]

[Chemical 4]

[Wherein R ¹ , R ² , R ³ , R ⁴ and R
⁵ has the same meaning as above] As shown in the above reaction scheme, the compound (I ′) of the present invention comprises a compound represented by the general formula (II) and a compound represented by the general formula (III). Can be obtained by reacting in a suitable solvent or without solvent. The reaction temperature is 90 to 16
It can be arbitrarily set within the range of 0 ° C. or the boiling point of the solvent. The solvent that can be used in the present invention is not particularly limited as long as it is a solvent that is substantially inert to the above reaction, but a solvent having a high boiling point such as toluene, xylene or mesitylene is preferable in view of the reaction temperature. Although the reaction time varies depending on the set conditions, it can be usually completed in 1 to 20 minutes. The ratio of the compound of the general formula (II) to the compound of the general formula (III) is not strictly limited, but is usually the compound of the general formula (II) per mol of the compound of the general formula (III). 0.5-2 mol, especially 0.9-1.1
It is preferably used within a molar range. The obtained product (I ′) can be isolated from the reaction mixture by a conventional method and, if necessary, can be easily purified by recrystallization, column chromatography or the like.

The compound of the general formula (II) used as a starting material in the above reaction can be produced by a method known per se, for example, the method described in US Pat. No. 2,582,128, or a production method analogous thereto. . More specifically, the compound of general formula (II) has the following reaction formula:

[0044]

[Chemical 5]

According to the formula [wherein R ³ , R ⁴ and R ⁵ have the same meanings as described above], the compound of the general formula (IV) can be added dropwise to formalin. The reaction temperature is preferably about room temperature. Although the reaction time varies depending on the set conditions, it can be normally completed in 0.1 to 10 hours. The product (II) can be isolated from the reaction mixture by a conventional method, and can be easily purified by recrystallization, distillation, column chromatography and the like.

The compound of the general formula (IV) used as a starting material in the production of the compound of the general formula (II) can be produced by a method known per se [eg, J. Org. Chem., 57 , 4521 (1992)]. Reference] or a manufacturing method similar thereto. The compound of the general formula (II) used as a starting material in the production of the compound of the general formula (I ′) is
Depending on the substituent, the following formula near room temperature:

[0047]

[Chemical 6]

It has been found that they are often in equilibrium with trimers as indicated by ## STR6 ## and may exist as mixtures thereof, and in some cases may exist entirely in trimers. There is. Therefore, the compound represented by the general formula (II) includes not only a monomer but also the above-mentioned trimer and a mixture of the monomer and the trimer. Therefore, these are represented by the structures and names of the monomers.

The compound of the general formula (III) used as a starting material for the compound of the present invention represented by the general formula (I ') can be prepared by a method known per se [eg, Chem. Pham. Bull. 31 (6), 1
896-1901 (1983)] or a manufacturing method similar thereto. More specifically, the compound of general formula (III) has the following reaction formula:

[0050]

[Chemical 7]

[In the formula, A represents a hydrogen atom or a group (for example, a tert-butyl group) which is easily eliminated under acidic conditions, and R ¹ ,
R ² has the same meaning as above], and can be produced by reacting the compound of general formula (V) with acetone in acetic anhydride using a small amount of sulfuric acid as a catalyst. Generally, the reaction temperature is preferably within the range of -25 ° C to room temperature. Although the reaction time varies depending on the set conditions, it can be usually completed in 1 to 100 hours. The ratio of acetone to the compound of the general formula (V) is usually 1 to 10 mol, preferably 1.5 to 3 mol per mol of the compound of the general formula (V). The obtained product (III) can be isolated from the reaction mixture by a conventional method, and can be easily purified by recrystallization, column chromatography or the like. (2) Production of the compound (I ″) of the present invention in which X is a group CH ₂
Method This production method has the following reaction formula:

[0052]

[Chemical 8]

[In the formula, R ⁶ represents a lower alkyl group,
R ³ , R ⁴ and R ⁵ have the same meanings as described above], and the first step for producing the first intermediate (VII), the following reaction formula:

[0054]

[Chemical 9]

[Wherein Y represents a halogen atom, R ³ , R ⁴ ,
R ⁵ and R ⁶ have the same meanings as above], and the second step of producing the second intermediate (IX) from the first intermediate (VII), and the following reaction formula:

[0056]

[Chemical 10]

[Wherein R ³ , R ⁴ , R ⁵ , R ⁶ and Y have the same meanings as described above], and the second intermediate (IX)
From the target compound (I ″).
In the first step, the compound represented by the general formula (IV) and the compound represented by the general formula (VI) are reacted in a suitable solvent or without solvent under a nitrogen stream to obtain a first intermediate. (VII) can be obtained. Examples of the solvent that can be used in this step include hydrocarbons such as benzene, toluene or xylene; alcohols such as methyl alcohol or ethyl alcohol; ethers such as diethyl ether, dioxane, tetrahydrofuran or dimethoxyethane; methylene chloride or chloroform. And halogenated hydrocarbons.

If necessary, a suitable catalyst may be added. For example, organic amines such as triethylamine or pyridine; metal alcoholates such as sodium ethylate; inorganic bases such as potassium carbonate or sodium carbonate; Copper or the like can be used. The amount of the catalyst used is not particularly limited, but it is preferably used in the range of 0.01 to 2 mol, and particularly 0.1 to 1 mol per mol of the compound of the general formula (IV). The reaction temperature is 0 to 100
It can be set arbitrarily within the range of ° C. Further, the reaction time may be variously changed depending on set conditions, but it can be usually completed in 2 to 48 hours. The obtained first intermediate (VII) can be isolated from the reaction mixture by a conventional method and, if necessary, can be easily purified by distillation or column chromatography.

Next, in the second step, the compound (VII) is dissolved in a suitable solvent and, if necessary, the reactivity of the substituted phenylacetic acid represented by the general formula (VIII) in the presence or absence of a base. The second intermediate (IX) can be obtained by reacting with inducibility. Examples of the solvent that can be used in this step include hydrocarbons such as benzene, toluene or xylene; ethers such as diethyl ether, dioxane, tetrahydrofuran or dimethoxyethane;
Halogenated hydrocarbons such as methylene chloride or chloroform; ketones such as acetone or methyl ethyl ketone; aprotic polar solvents such as acetonitrile, N, N-dimethylformamide or N, N-dimethylacetamide, and the like.

Examples of the reactive derivative of the substituted phenylacetic acid represented by the general formula (VIII) include acid anhydrides, acid chlorides, acid bromides, active esters and the like. Examples of the base include triethylamine, pyridine, N, N
-Organic amines such as dimethylaniline, N-methylmorpholine or quinoline, or inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate and the like can be used. The amount of the base used is not particularly limited, but it is preferably used within a range of 0.5 to 2 mol, particularly 0.9 to 1.1 mol, per 1 mol of the compound of the general formula (VII). The reaction temperature is -10
It can be arbitrarily set within a range of up to 50 ° C. Although the reaction time varies depending on the set conditions, it can be usually completed in 1 to 24 hours. The second intermediate (IX) can be isolated from the reaction mixture by a conventional method and, if necessary, can be easily purified by recrystallization, column chromatography or the like.

In the third step, the second intermediate (IX)
The compound (I ") of the present invention can be obtained by ring closure of the compound (I") in a suitable solvent in the presence of a suitable reaction auxiliary. Examples of the solvent that can be used include benzene, toluene and xylene. Hydrocarbons; alcohols such as methyl alcohol or ethyl alcohol; ethers such as dioxane, tetrahydrofuran or dimethoxyethane; halogenated hydrocarbons such as methylene chloride or chloroform; ketones such as acetone or methyl ethyl ketone; acetonitrile, N, N- Examples thereof include aprotic polar solvents such as dimethylformamide, N, N-dimethylacetamide and dimethylsulfoxide.

Examples of the reaction aid include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate, or metal alcoholates such as sodium methylate, sodium ethylate or potassium tertiary butoxide. Classes and the like can be used. The reaction temperature is not particularly limited and can be arbitrarily set within the range of room temperature to the boiling point of the solvent. Although the reaction time varies depending on the set conditions, it can usually be completed in 10 to 120 minutes. The obtained target compound (I ") can be isolated from the reaction mixture by a conventional method, and if necessary, can be easily purified by recrystallization, column chromatography or the like.

When the compound represented by the general formula (I) of the present invention is used as a herbicide, it is mixed with a carrier or a diluent, an additive, an auxiliary agent, etc. by a known method and usually used as an agricultural chemical. Formulation forms such as powders, granules,
It can be used by preparing it as a wettable powder, an emulsion, a water solvent or a flowable agent. Further, it can be used as a mixture or in combination with other pesticides such as fungicides, insecticides, acaricides, herbicides, plant growth regulators, fertilizers and soil conditioners. Especially when mixed with other herbicides,
Not only can the amount of drug used be reduced and labor saving can be achieved, but also a higher effect can be expected due to the broadening of the herbicidal spectrum due to the synergistic action of both drugs and the synergistic action.

The carriers or diluents used in the preparation include solid or liquid carriers generally used. Examples of the solid carrier include clays represented by kaolinite group, montmorillonite group, illite group, polygloskite group, etc .; specifically, pyrophyllite, attapulgite, sepiolite, kaolinite, bentonite, vermiculite, mica, talc, etc. ; Other inorganic substances such as gypsum, calcium carbonate, dolomite, diatomaceous earth, magnesium lime, apatite, zeolite, silicic acid anhydride, synthetic calcium silicate; soybean flour, tobacco flour, walnut flour, wheat flour, wood flour, starch , Vegetable organic substances such as crystalline cellulose; synthetic or natural polymer compounds such as coumarone resin, petroleum resin, alkyd resin, polyvinyl chloride, polyalkylene glycol, ketone resin, ester gum, cobal gum, dammal gum; carnauba wax, beeswax Wax, etc. Or urea and the like.

Suitable liquid carriers include, for example, paraffinic or naphthenic hydrocarbons such as kerosene, mineral oil, spindle oil and white oil; aromatic hydrocarbons such as xylene, ethylbenzene, cumene or methylnaphthalene; trichloroethylene and monochloro. Chlorinated hydrocarbons such as benzene or orthochlorotoluene; ethers such as dioxane or tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, acetophenone or isophorone;
Esters such as ethyl acetate, amyl acetate, ethylene glycol acetate, diethylene glycol acetate, dibutyl maleate or diethyl succinate; alcohols such as methanol, n-hexanol, ethylene glycol, diethylene glycol, cyclohexanol or benzyl alcohol; ethylene glycol ethyl ether Or ether alcohols such as diethylene glycol butyl ether; polar solvents such as dimethylformamide or dimethylsulfoxide; or water.

In addition, emulsification, dispersion, wetting, spreading, spreading, binding, control of disintegration, stabilization of active ingredient of the compound of the present invention,
Surfactants and other auxiliaries may be used for the purpose of improving fluidity, preventing rust and preventing freezing. As the surfactant to be used, any of nonionic, anionic, cationic and zwitterionic can be used, but usually a nonionic and / or anionic one is used. .
Suitable nonionic surfactants include, for example, compounds obtained by polymerizing addition of ethylene oxide to a higher alcohol such as lauryl alcohol, stearyl alcohol or oleyl alcohol; polymerization addition of ethylene oxide to an alkylnaphthol such as butylnaphthol or octylnaphthol. Examples thereof include compounds; compounds obtained by polymerizing addition of ethylene oxide to higher fatty acids such as palmitic acid, stearic acid or oleic acid; or higher fatty acid esters of polyhydric alcohols such as sorbitan and compounds obtained by polymerizing addition of ethylene oxide.

Suitable anionic surfactants include, for example, alkyl sulfate salts such as sodium lauryl sulfate or oleyl alcohol sulfate amine salt;
Sodium sulfosuccinate dioctyl ester or 2
-Alkyl sulfonates such as sodium ethylhexene sulfonate; sodium isopropylnaphthalene sulfonate, sodium methylenebisnaphthalene sulfonate,
Examples thereof include aryl sulfonates such as sodium lignin sulfonate and sodium dodecylbenzene sulfonate. Further, the herbicide of the present invention improves the properties of the preparation and, for the purpose of enhancing the effect, polymer compounds such as casein, gelatin, albumin, glue, sodium alginate, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose or polyvinyl alcohol. Other auxiliary agents can be used in combination.

The above-mentioned carrier and various auxiliary agents are appropriately used alone or in combination depending on the purpose in consideration of the formulation system of the preparation, the application scene and the like. The content of the active ingredient of the compound of the present invention in the various dosage forms thus obtained varies depending on the dosage form, but is usually 0.1 to 99% by weight, preferably 1 to 80% by weight.
Weight percent is most suitable. In the case of a wettable powder, for example, the active ingredient compound is usually contained in an amount of 25 to 90%, and the rest is a solid carrier and a dispersion wetting agent, and a protective colloid agent, a defoaming agent and the like are added if necessary. In the case of granules, for example, the active ingredient compound is usually contained in an amount of 1 to 35% by weight, and the balance is a solid carrier and a surfactant. The active ingredient compound is either uniformly mixed with the solid carrier, or is evenly fixed or adsorbed on the surface of the solid carrier, and the particle diameter is about 0.2 to 1.5 mm. In the case of an emulsion, for example, the active ingredient compound is usually contained in an amount of 5 to 30% by weight, which contains about 5 to 20% by weight of an emulsifier, and the balance is a liquid carrier. Anti-corrosion agent is added. In the case of a flowable agent, for example, the active ingredient compound is usually 5
It is contained in an amount of 50% by weight, and contains 3 to 10% by weight of a dispersion wetting agent, and the balance is water, and a protective colloid agent, a preservative, an antifoaming agent and the like are added if necessary.

The compound derivative of the general formula (I) of the present invention can be used as a herbicide as the compound itself or in any of the above-mentioned preparation forms. The composition of the present invention can be applied to various weeds from the pre-emergence period to the growing season, which grow on agricultural lands such as paddy fields and upland fields, and non-agricultural lands. The application rate is 0.1 to 10 per 1 ha as the active ingredient amount,
It is about 000 g, preferably about 1 to 5,000 g. The application rate can be appropriately selected and changed depending on the type of weed, the growth stage, the place of application and the weather.

The compound represented by the general formula (I) of the present invention and a herbicide containing the compound as an active ingredient have herbicidal activity against various weeds, but are highly safe for cultivated crops. Have. That is, the compound of the present invention and a herbicide containing the compound as an active ingredient are, for example, barnyard grass, paddy snail, konjac, yellow sedge, which occur in paddy fields.
It exhibits excellent herbicidal effect with extremely low dose over a wide range from germination to growing season of annual weeds such as Azena and Abenome and perennial weeds such as firefly, matsubai, herring mold and cypress, while simultaneously transplanting paddy rice and direct watering. It is highly safe for paddy rice and dry-seeded rice. In addition, various weeds that are also problematic in the field, for example, broadleaf weeds such as willow tree, Aobiyu and Shiroza, perennial and annual perennial cyperaceae weeds such as yellow sedge, yellow sedge, Himekugu, cyperaceae and Kogomegayatsu, weegrass, swordgrass, elogue, It shows a high herbicidal effect by soil treatment or foliar treatment against grass weeds such as bluegrass, Johnsongrass, wild oats, and bluegrass, and at the same time soybean, cotton, sugar beet, rapeseed, sunflower, corn, upland rice or wheat. Shows high safety.

Further, it can be used not only in paddy fields and upland fields but also in orchards, mulberry fields, lawns and non-agricultural fields.
Furthermore, by using the compound of the present invention as a mixture with a known compound, each compound alone exhibits an excellent herbicidal effect against weeds difficult to control, and a synergistic herbicidal effect makes it difficult to control with a single agent. Effectively control various weeds even in the dosage, and highly useful for agriculture showing high safety against cultivated plants such as paddy rice, soybean, cotton, sugar beet, rapeseed, sunflower, corn, upland rice or wheat. A herbicide can be provided. The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.

[0072]

【Example】

Production Example of Compound (I) of the Present Invention (1) Production Example 1: Production of Compound (I ') i) Production of 1 -methyl-1- (3-thienyl) ethylamine 9.9 g of anhydrous cerium chloride and tetrahydrofuran 80
The mixture was suspended in ml, the suspension was stirred under a nitrogen atmosphere overnight, cooled to -50 ° C or lower, and 26.6 ml of 1.5M methyllithium ether solution was added. 30 at this temperature
After stirring for 1 minute, the mixture was cooled to −65 ° C., 2 ml of a tetrahydrofuran solution containing 1.42 g of 3-cyanothiophene was added, and this was left to react for 5 hours. 2 in the reaction mixture
After adding 25 ml of 5% aqueous ammonia and filtering, the mixture was extracted with diethyl ether. The organic layer was washed with saturated saline and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 1.0 g of the title compound as an oil. ii) Preparation of N-methylene-1-methyl- (3-thienyl) ethylamine 1-Methyl-1-prepared in the same manner as in i) above.
0.83 g of (3-thienyl) ethylamine was gently added to formalin (37% HCHO aqueous solution) 0.68 at room temperature.
g. This was left to react for 2 hours. A saturated sodium hydrogen carbonate solution was added to the reaction mixture, and the mixture was extracted with diethyl ether. The organic layer was washed with saturated saline and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 1.06 g of the title compound as an oil. iii) 6-methyl-3- [1-methyl-1- (3-thienyl) ethyl] -5-phenyl-2,3-dihydro-4
Production of H -1,3-oxazin-4-one (Compound No. 9) N-methylene-1- produced by the same method as in ii) above.
Methyl-1- (3-thienyl) ethylamine 0.61 g
When 5-phenyl-2,2,6-trimethyl--2 H, 4 H -
2 ml of xylene was added to a mixture of 0.72 g of 1,3-dioxin-4-one, and the mixture was heated under reflux for 30 minutes for reaction.
The solvent was distilled off under reduced pressure, and the residue was purified by silica gel chromatography to obtain 0.79 g of the title compound.

Preparation Example 2: i) Preparation of N-methylene-1- (2-furyl) -1-methylethylamine 1- (2-furyl) -1-methylethylamine 0.69 g
Was gently added to 0.54 g of formalin (37% HCHO aqueous solution) at room temperature. This was left to react for 2 hours. A saturated sodium hydrogen carbonate solution was added to the reaction mixture, and the mixture was extracted with diethyl ether. The organic layer was washed with saturated saline and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 0.75 g of the title compound as an oil. ii) 6- methyl-3- [1- (2-furyl) -1-methylethyl] -5-phenyl-2,3-dihydro -4 H-1,3-oxazin-4-one (Compound
Production of No. 10) N-methylene-1- produced by the same method as i) above.
(2-furyl) -1-methylethylamine 0.50 g and 5
- phenyl-2,2,6-trimethyl--2 H, 4 H -1,3
-Dioxin-4-one To a mixture of 0.61 g, 2 ml of xylene was added, and the mixture was heated under reflux for 30 minutes for reaction. The solvent was evaporated under reduced pressure, and the residue was purified by silica gel chromatography to give the title compound (0.54 g).

Production Example 3: 6-Methyl-3- [1-methyl-1- (2-pyridyl) ethyl] -5-phenyl-2,3
- dihydro -4 H-1,3-oxazin-4-one prepared N- methylene-1-methyl (Compound No.1) -1- (2-pyridyl) ethylamine 0.53g of 5-phenyl-2,2 , 6-trimethyl -2 H, 4 H-1,3-dioxin-4-one 0.5
Xylene (2 ml) was added to the mixture (3 g), and the mixture was heated under reflux for 30 minutes for reaction. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel chromatography to give the title compound 0.35.
g was obtained.

Production Example 4: 6-Methyl-3- [1- (2-
Chloro-6-pyridyl) -1-methylethyl] -5-phenyl-2,3-dihydro -4 H-1,3-oxazine -
Preparation of 4-one (Compound No. 4) N-methylene-1- (2-chloro-6-pyridyl) -1-
0.55 g of methylethylamine and 5-phenyl-2,2,
6-trimethyl -2 H, 4H-1,3- dioxin-4
ON To 0.65 g of mixture, add 3 ml of xylene to 30
The mixture was heated to reflux for a reaction time. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel chromatography to obtain 0.70 g of the title compound.

Production Example 5: 6-methyl-3- [1- (2,6
-Dichloro-4-pyridyl) -1-methylethyl] -5
- phenyl-2,3-dihydro -4 H-1,3-oxazin-4-one (Compound No.5) To a solution of N- methylene-1- (2,6-dichloro-4-pyridyl)
-1-methylethylamine 0.70 g and 5-phenyl-
2,2,6-trimethyl--2 H, 4 H -1,3- dioxin-4 was a mixture of the on 0.65g to xylene 3ml was heated to reflux for 30 minutes was added to the reaction. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel chromatography to obtain 0.72 g of the title compound.

Production Example 6: 6-Methyl-3- [1- (2-
Benzothiazolyl) -1-methylethyl] -5-phenyl-2,3-dihydro -4 H-1,3-oxazin-4
Preparation of On (Compound No. 19) 0.50 g of N-methylene-1- (2-benzothiazolyl) -1-methylethylamine and 5-phenyl-2,2,6-
Trimethyl -2 H, 4 H -1,3- dioxin-4 was a mixture of the on 0.57g to xylene 2ml heated under reflux for 30 minutes was added to the reaction. The solvent was evaporated under reduced pressure, and the residue was purified by silica gel chromatography to give the title compound (0.20 g).

Production Example 7: 6-Methyl-3- [1-methyl-1- (2-quinolyl) ethyl] -5-phenyl-2,3
- dihydro -4 H-1,3-oxazin-4-one prepared N- methylene-1-methyl (Compound No.27) -1- (2-quinolyl) ethylamine 0.63g of 5-phenyl-2,2 , 6-trimethyl -2 H, 4 H-1,3-dioxin-4-one 0.6
3 ml of xylene was added to 5 g of the mixture, and the mixture was heated under reflux for 30 minutes to react. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel chromatography to give the title compound 0.65.
g was obtained.

(2) Production of Compound (I '') Production Example 8: i) Production of 4- [1- (2-chloro-6-pyridyl) -1-methylethylamine] -2-butanone Methyl vinyl ketone 0 1- (2-chloro-6 to 0.41 g
-Pyridyl) -1-methylethylamine (1.0 g) was added, and the mixture was stirred at room temperature for 2 days under a nitrogen atmosphere. After completion of the reaction, low-boiling substances were distilled off under reduced pressure to give an oily title compound 1.
4 g was obtained. ii) Production of N- [1- (2-chloro-6-pyridyl) -1-methylethyl] -N- (3-oxobutyl) phenylacetamide 4- [1-] produced by the same method as in i) above. (2-Chloro-6-pyridyl) -1-methylethylamine] -2
-Butanone 1.38 g of acetone solution 10 ml was added with potassium carbonate 0.97 g, and phenylacetic acid chloride 1.08 g was added dropwise under ice cooling. The temperature was gradually raised to room temperature and the mixture was stirred for 3 hours. After completion of the reaction, the reaction solution was filtered and the solvent was distilled off under reduced pressure. Water was added to the residue, and the mixture was extracted with diethyl ether. The organic layer was washed with saturated saline and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel chromatography to obtain 1.10 g of the title compound. iii) 4-methyl-1- [1- (2-chloro-6-pyridyl) -1-methylethyl] -3-phenyl-1,2,5,
6-Tetrahydropyridin-2-one (Compound No. 3
Production of 23) N- [1- (2-chloro-6-pyridyl) -1-methylethyl] -N- (3- produced by the same method as ii) above.
Oxobutyl) phenylacetamide (1.08 g) in ethyl alcohol (7 ml) was added with potassium hydroxide (0.05).
g of powder was added, and the mixture was heated under reflux for 1.5 hours. Then, after returning to room temperature and distilling off ethyl alcohol under reduced pressure,
Water was added to the residue, and the mixture was extracted with diethyl ether. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel chromatography to give the title compound (0.66 g)
Got

Production Example 9: 4-methyl-1- [1- (2,6
-Dichloro-4-pyridyl) -1-methylethyl] -3
-Phenyl-1,2,5,6-tetrahydropyridine-2
Preparation of N-one (Compound No. 324) N- [1- (2,6-dichloro-4-pyridyl) -1-methylethyl] -N- (3-oxobutyl) phenylacetamide 0.86 g of ethyl alcohol solution 7 ml
To this, 0.03 g of potassium hydroxide powder was added, and the mixture was heated under reflux for 2 hours. Then, the temperature was returned to room temperature, ethyl alcohol was distilled off under reduced pressure, water was added to the residue, and the mixture was extracted with diethyl ether. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure.
The obtained residue was purified by silica gel chromatography to give the title compound (0.40 g).

Production Example 10: 4-methyl-1- [1- (2
-Chloro-4-trifluoromethyl-6-pyridyl)-
1-Methylethyl] -3-phenyl-1,2,5,6-tetrahydropyridin-2-one (Compound No. 325)
Production of N- [1- (2-chloro-4-trifluoromethyl-6
-Pyridyl) -1-methylethyl] -N- (3-oxobutyl) phenylacetamide To 7 ml of an ethyl alcohol solution containing 1.00 g of powder was added 0.03 g of potassium hydroxide powder, and the mixture was heated under reflux for 1.5 hours. Then, the temperature was returned to room temperature, ethyl alcohol was distilled off under reduced pressure, water was added to the residue, and the mixture was extracted with diethyl ether. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel chromatography to give the title compound (0.33 g).

Production Example 11: 4-methyl-1- [1- (2
-Trifluoromethyl-6-pyridyl) -1-methylethyl] -3-phenyl-1,2,5,6-tetrahydropyridin-2-one (Compound No. 326) Production N- [1- (2- Trifluoromethyl-6-pyridyl)-
1-Methylethyl] -N- (3-oxobutyl) phenylacetamide 1.10 g of ethyl alcohol solution 7
Add 0.04 g of potassium hydroxide powder to ml and add 1.5
Heated to reflux for hours. Then, the temperature was returned to room temperature, ethyl alcohol was distilled off under reduced pressure, water was added to the residue, and the mixture was extracted with diethyl ether. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel chromatography to give the title compound (0.80 g).

Production Example 12: 4-methyl-1- [1- (5
-Chloro-2-benzothiazolyl) -1-methylethyl] -3-phenyl-1,2,5,6-tetrahydropyridin-2-one (Compound No. 340) N- [1- (5-chloro- 2-benzothiazolyl) -1-
Methylethyl] -N- (3-oxobutyl) phenylacetamide 0.25 g ethyl alcohol solution 3 ml
To this, 0.01 g of potassium hydroxide powder was added, and the mixture was heated under reflux for 1.5 hours. Then, the temperature was returned to room temperature, ethyl alcohol was distilled off under reduced pressure, water was added to the residue, and the mixture was extracted with diethyl ether. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel chromatography to give the title compound (0.03 g).

Production Example 13: 4-methyl-1- [1- (2
-Benzofuranyl) -1-methylethyl] -3-phenyl-1,2,5,6-tetrahydropyridin-2-one (Compound No. 345): N- [1- (2-benzofuranyl) -1- Methyl ethyl]
-N- (3-oxobutyl) phenylacetamide 2.
To 14 ml of an ethyl alcohol solution (00 g) was added 0.09 g of potassium hydroxide powder, and the mixture was heated under reflux for 1.5 hours. Then, the temperature was returned to room temperature, ethyl alcohol was distilled off under reduced pressure, water was added to the residue, and the mixture was extracted with diethyl ether. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel chromatography to give the title compound (0.86 g). The melting points of the substances produced by the above Production Examples 1 to 13 and the substances produced by the same method are shown in Table 1 above, and the ¹ H-NMR peak values are shown in Table 2 below.

[0085]

[Table 27]

[0086]

[Table 28]

[0087]

[Table 29]

Next, several modes of formulation examples using the compound of the present invention will be shown. The "parts" in the following preparations are based on weight. Formulation Example 1 (Emulsion) Compound No. 1 20 parts Xylene 50 parts Cyclohexanone 20 parts Calcium dodecylbenzene sulfonate 5 parts Polyoxyethylene styryl phenyl ether 5 parts The above components were uniformly mixed and dissolved to obtain 100 parts of an emulsion. Formulation Example 2 (Wettable powder) Compound No. 2 20 parts Clay 70 parts Lignin sulfonate calcium 7 parts Alkylnaphthalene sulfonate formalin condensate 3 parts The above components are mixed and pulverized with a jet mill to obtain 100 parts wettable powder. It was

Formulation Example 3 (flowable agent) Compound No. 3 20 parts Sulfosuccinic acid di-2-ethylhexyl ester sodium salt 2 parts Polyoxyethylene nonylphenyl ether 2 parts Defoamer 0.5 part Propylene glycol 5 parts Water 70. Five parts or more were uniformly pulverized and mixed with a wet ball mill to obtain 100 parts of a flowable agent. Herbicides containing the compound of the present invention can be prepared according to the above-mentioned preparation examples. Next, the herbicidal effect of the compound of the present invention will be described with reference to test examples.

Test Example 1 (Medicinal efficacy / medicine in paddy soil treatment
Harm test) Fill a 130 cm ² plastic pot with paddy soil,
A proper amount of water and chemical fertilizer were added and kneaded to form a paddy field. Rice seedlings (cultivar: Koshihikari), which had been grown in a greenhouse so that the number of leaves was 2 in advance, were transplanted to each plant as 1 strain per pot, and further, various plants such as Nobie, Konagi, Azena and Firefly were planted. A certain amount of pups were sowed and submerged at a depth of 3 cm. The next day, the compounds of the present invention shown in Table 3 below were prepared into wettable powders according to Formulation Example 2, and the amount of active ingredient was 5 kg or 1 per ha.
The mixture was diluted with an appropriate amount of water so that the weight became kg, and then treated dropwise with a pipette. Twenty-one days after the chemical treatment, the herbicidal effect on each weed and the degree of chemical damage to paddy rice were determined according to the following criteria. The results are shown in Table 3.

[0091]

[Table 30]

[0092]

[Table 31]

[0093]

[Table 32]

Test Example 2 (Test of herbicidal effect by treatment of paddy soil
Test) Fill a 130 cm ² plastic pot with paddy soil,
A proper amount of water and chemical fertilizer were added and kneaded to form a paddy field. A certain amount of each species of Nobie, Konagi, Azena and Firefly were sown on this, and the water was flooded to a depth of 3 cm. Next day, 4th below
The compound of the present invention shown in the table was prepared as a wettable powder according to Formulation Example 2, diluted with an appropriate amount of water so that the amount of the active ingredient was 5 kg or 1 kg per ha, and the solution was added dropwise using a pipette. Twenty-one days after the chemical treatment, the herbicidal effect on each weed and the degree of phytotoxicity to paddy rice were determined according to the criteria of Test Example 1. The results are shown in Table 4.

[0095]

[Table 33]

[0096]

[Table 34]

Test Example 3 (Medicinal efficacy / medicine in treatment of paddy foliage
Harm test) Fill a 130 cm ² plastic pot with paddy soil,
A proper amount of water and chemical fertilizer were added and kneaded to form a paddy field. Rice seedlings (cultivar: Koshihikari), which had been grown in a greenhouse so that the number of leaves was 2 in advance, were transplanted to each plant as 1 strain per pot, and further, various plants such as Nobie, Konagi, Azena and Firefly were planted. A certain amount of pups were sowed and submerged at a depth of 3 cm. After growing Nobie in the greenhouse until the leaf stage reached the 1.5 leaf stage, the compounds of the present invention shown in Table 5 below were prepared as wettable powders according to Formulation Example 2 to obtain 5 kg or 1 kg of active ingredient per ha. It was diluted with an appropriate amount of water so that it was added dropwise and treated with a pipette. Twenty-one days after the chemical treatment, the herbicidal effect on each weed and the degree of chemical damage to paddy rice were determined according to the criteria of Test Example 1. The results are shown in Table 5.

[0098]

[Table 35]

Test Example 4 (Test of herbicidal effect by treatment of foliage of paddy field
Test) Fill a 130 cm ² plastic pot with paddy soil,
A proper amount of water and chemical fertilizer were added and kneaded to form a paddy field. A certain amount of each species of Nobie, Konagi, Azena and Firefly were sown on this, and the water was flooded to a depth of 3 cm. Novie is 1.5
After growing in the greenhouse until the leaf stage, the compounds of the present invention shown in Table 6 below were prepared into wettable powders according to Formulation Example 2, and an appropriate amount of the active ingredient was adjusted to 5 kg or 1 kg per ha. It was diluted with water and treated dropwise with a pipette. Twenty-one days after the chemical treatment, the herbicidal effect on each weed and the degree of chemical damage to paddy rice were determined according to the criteria of Test Example 1.
The results are shown in Table 6.

[0100]

[Table 36]

[0101]

[Table 37]

[0102]

The present invention provides a novel cyclic amide derivative having high herbicidal activity and excellent selectivity, and a herbicide containing the same as an active ingredient. The compound is characterized in that the 3-position is substituted with a tertiary alkyl group or a tertiary aralkyl group, and the 1-position is substituted with a tertiary carbon substituted with a heterocycle, whereby the above-mentioned characteristics are obtained. It seems to demonstrate.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical indication location C07D 413/06 241 261 307 319 333 A01N 43/86 101 (72) Inventor Shuji Mukata Central Ami-machi, Inashiki-gun, Ibaraki Prefecture 8-3-1, Mitsubishi Petrochemical Co., Ltd. Tsukuba Research Institute

Claims (2)

[Claims] 1. The following general formula (I): [Wherein R ¹ is a lower alkyl group, a lower alkenyl group, a lower alkynyl group, an optionally substituted aryl group or an optionally substituted aralkyl group, R ² is a hydrogen atom or a lower alkyl group, ³ each occurrence is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkyl group or a lower haloalkoxy be optionally substituted with a group, or a benzene ring and condensed may 5 or even six membered A cyclic heterocyclic group, R ⁴ and R ⁵ each independently represent a lower alkyl group, and X represents an oxygen atom or a group CH _2. ] 2. General formula (I): [Wherein R ¹ is a lower alkyl group, a lower alkenyl group, a lower alkynyl group, an optionally substituted aryl group or an optionally substituted aralkyl group, R ² is a hydrogen atom or a lower alkyl group, ³ each occurrence is a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkyl group or a lower haloalkoxy be optionally substituted with a group, or a benzene ring and condensed may 5 or even six membered A heterocyclic group of a ring, R ⁴ and R ⁵ independently of each other represent a lower alkyl group, and X represents an oxygen atom or a group CH ₂ ] as an active ingredient. Herbicide to do.