JPH0625160A - Cyclic amide compounds, their production and herbicide containing the compounds - Google Patents

Abstract

PURPOSE:To provide the novel compound useful as a herbicide having excellent herbicidal effect and selectivity. CONSTITUTION:A compound of formula I [R<1> is phenyl; R<2> is H, alkyl; R<3> is group of formula II (D is O, S, etc.,); (m) is 1,2], e.g. 1-[1-(benzothiazol-2-yl)-1- methylethyl]-4-methyl-3-phenyl-3-pyrroline-2-one. The compound of formula I is obtained by dehydratively condensing a compound of formula III in the presence of a base (e.g. sodium hydride) in a solvent (e.g. THF) at -80 to 200 deg.C for 0.01-3hr. The compound of formula I does not give chemical damages to crops, can selectively kill only injurious weeds, and is effective for the weeds such as Panicum crusgalli L., Scirpus and Aponogeton.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel cyclic amide compound represented by the following general formula (I), a process for producing them, a herbicide containing them and an intermediate compound for producing them.

[0002]

Conventionally, there has been a strong demand for a herbicide that selectively kills only harmful weeds without giving any phytotoxicity to crops, and various studies have been conducted to find such herbs.
Although published, they are not always satisfactory and there is a desire for the emergence of even better herbicides.

On the other hand, Japanese Unexamined Patent Publication (Kokai) No. 3-204855 describes a cyclic amide derivative having herbicidal activity, which is different from the compound of the present invention represented by the general formula (I) described later.

[0004]

Means for Solving the Problems As a result of intensive investigations by the present inventors on a cyclic amide compound in order to find an excellent herbicide, the compound represented by the following general formula (I) has an excellent herbicidal effect and selectivity. The present invention has been completed based on the finding that

[0005]

DISCLOSURE OF THE INVENTION That is, the present invention is represented by the general formula (I);

[0006]

[Chemical 6]

The present invention relates to cyclic amide compounds represented by :, a method for producing them, herbicides containing them, and intermediate compounds for producing them.

[0008]

[Chemical 7]

In the general formula (I), the substituent of the optionally substituted phenyl group contained in R ¹ is a halogen atom, an alkyl group optionally substituted with a halogen atom, or a halogen atom. A good alkoxy group, an alkylthio group optionally substituted with a halogen atom, an alkylsulfonyl group optionally substituted with a halogen atom and the like,

[0010]

[Chemical 8]

As the substituent of the above, in addition to the same substituents as those contained in R ¹ , an aryl group which may be substituted with a halogen atom or a halogenoalkyl group, a halogen atom or a halogenoalkyl group may be substituted. An aryloxy group etc. are mentioned. Examples of the aryl group which may be substituted include a phenyl group and a pyridyl group, and examples of the aryloxy group which may be substituted include a phenoxy group, a pyridyloxy group and a trifluoromethylpyridyloxy group. Groups and the like.
The number of substitutions of these substituents may be 1 or 2 or more, and in the case of 2 or more, the substituents may be the same or different.

In the general formula (I), the alkyl group and the alkyl moiety contained in R ¹ , R ² , R ³ and R ⁴ have a carbon number of 1 to 8 and are linear or branched. For example, methyl group, ethyl group, propyl group, isopropyl group,
Examples thereof include tertiary butyl group, pentyl group and octyl group. Further, examples of the halogen atom contained in R ¹ , R ² and R ³ and the halogen atom as a substituent include fluorine, chlorine, bromine and iodine atoms. The number of substitution of the halogen atom as a substituent may be 1 or 2 or more, and when it is 2 or more, they may be the same or different.

The compound represented by the general formula (I) is
For example, it can be produced by a method such as the reaction [A].

[0014]

[Chemical 9]

In the reaction [A], R ¹ , R ² , R ³ and m are as described above.

The reaction [A] is usually carried out in the presence of a base and a solvent. Examples of the base include metal hydroxides such as sodium hydroxide and potassium hydroxide; metal hydrides such as sodium hydride and potassium hydride; metal alcoholates such as sodium methylate, sodium ethylate and potassium tertiary butoxide. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; cyclic or acyclic aliphatic hydrocarbons such as carbon tetrachloride, methylene chloride, dichloroethane, trichloroethane, hexane, and cyclohexane. Ethers such as diethyl ether, dioxane and tetrahydrofuran; Esters such as methyl acetate and ethyl acetate; Dimethyl sulfoxide, sulfolane, dimethylacetamide, dimethylformamide, N
Aprotic polar solvents such as methylpyrrolidone and pyridine; alcohols such as methanol and ethanol; water and the like.

The reaction temperature of the reaction [A] is usually -80 to +2.
The temperature is 00 ° C, preferably 0 to 100 ° C, and the reaction time is generally 0.01 to 3 hours, preferably 0.01 to 1 hour.

The compound represented by the general formula (II) can be produced, for example, by the method of the reaction [B].

[0019]

[Chemical 10]

In the reaction [B], R ¹ , R ² , R ³ and m are as described above, M is a sodium atom or potassium atom, X is each atom of chlorine, bromine or iodine, and Z is Z.
Is each atom of fluorine, chlorine or bromine or an --OH group. However, the formula ^R 3 -CN ^{R 3} s, except those substituted by a bromine atom or an iodine atom.

The compound represented by the general formula (VII) in the above reaction [B] can be produced, for example, by a method such as reactions [C] to [F].

[0022]

[Chemical 11]

[0023]

[Chemical 12]

[0024]

[Chemical 13]

[0025]

[Chemical 14]

In the reactions [C] to [F], D and X are as described above, R ⁴ ′ is an alkyl group, R ⁵ is a hydrogen atom, a halogen atom, or an alkyl which may be substituted with a halogen atom. Group, an alkoxy group which may be substituted with a halogen atom, an alkylthio group which may be substituted with a halogen atom,
An alkylsulfonyl group optionally substituted with a halogen atom, an aryl group optionally substituted with a halogen atom or a halogenoalkyl group, or an aryloxy group optionally substituted with a halogen atom or a halogenoalkyl group, and Y
Is a chlorine atom or a bromine atom, n is an integer of 1 to 4, and 1 is an integer of 1 to 3. In addition, when n and 1 are integers greater than or equal to 2, R < ⁵ > may be same or different.

In the above reaction [B], a compound of the general formula (VI)
The compound represented by the formula (I) can also be produced by a method such as the reaction [G] or [H], and the compound represented by the general formula (IV) can also be produced by a method such as the reaction [I]. .

[0028]

[Chemical 15]

[0029]

[Chemical 16]

In the reactions [G] and [H], D, R ⁵ , X and n are as described above, in the reaction [I], R ³ is as described above, Hal is a halogen atom, R ⁶ is a halogen atom, an alkoxy group, a benzyloxy group or a phenoxy group.

In the reactions [C] and [G], when D is a sulfur atom among the compounds represented by the general formula (VIII), it can be produced by a method such as the reaction [J]. it can.

[0032]

[Chemical 17]

In the reaction [J], Hal, R ⁵ and n are as described above, and R ⁷ is hydrogen atom, chlorine atom, phenyl group, -OH group, -NH ₂ group or

[0034]

[Chemical 18]

Solvents or inert solvents used in the above reactions [B] to [H] and [J] are aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; chloroform, carbon tetrachloride and methylene chloride. Cyclic or acyclic aliphatic hydrocarbons such as dichloroethane, trichloroethane, hexane and cyclohexane; ethers such as diethyl ether, dioxane and tetrahydrofuran; nitriles such as acetonitrile, propionitrile and acrylonitrile, methyl acetate, acetic acid Esters such as ethyl; dimethylsulfoxide, sulfolane, dimethylacetamide, dimethylformamide,
Aprotic polar solvents such as N-methylpyrrolidone and pyridine; ketones such as acetone and methyl ethyl ketone; alcohols such as methanol, ethanol and tert-butanol; organic or inorganic acids such as acetic acid, formic acid and hydrochloric acid. Suitably selected from water and the like, the base being a carbonate such as potassium carbonate or sodium carbonate; a bicarbonate such as potassium bicarbonate or sodium bicarbonate; a metal hydroxide such as potassium hydroxide or sodium hydroxide. Tertiary amines such as triethylamine; pyridine, pyridines such as 4-dimethylaminopyridine, and the like, and the inert gas is appropriately selected from gases such as argon, helium, and nitrogen. Also, as a dehydrating agent,
N, N′-dicyclohexylcarbodiimide and the like, the catalyst includes 2,2′-azobisisobutyronitrile, metachloroperbenzoic acid, light and the like, and the acid includes formic acid, hydrochloric acid and hydrogen bromide. Acids, sulfuric acid, etc. are mentioned, alkalis include potassium hydroxide, sodium hydroxide, etc., and peroxides include hydrogen peroxide, etc.

Further, various reaction conditions in the above reaction [I] are appropriately selected from the reactions described in JP-A-3-204855 or other similar reactions.

The compound of the present invention is useful as an active ingredient of a herbicide, but the range of application of the herbicide containing the compound of the present invention is paddy field, farmland such as upland, mountain forest, farm road, ground,
There are a wide variety of non-agricultural lands such as factory premises, and the application method can be appropriately selected from soil treatment and foliage treatment.

The compound of the present invention is usually mixed with various auxiliaries and is in the form of granules, wettable powders, wettable powders, aqueous suspensions, oily suspensions, aqueous solutions, emulsions, tablets, capsules and the like. To be used as a preparation. In this case, the compounding ratio of the compound of the present invention and various auxiliary agents is appropriately selected within the range of 1: 99.5 to 90:10. Examples of the various auxiliary agents mentioned above include solid carriers, surfactants, spreading agents, extenders, vegetable oils, mineral oils, thickeners,
In addition to anti-settling agents, anti-freezing agents, solvents, dispersion stabilizers, phytotoxicity reducing agents, antifungal agents and the like, various auxiliary agents usually used in agricultural chemical formulations can be mentioned.

The application rate of the herbicide of the present invention cannot be unconditionally defined due to differences in meteorological conditions, soil conditions, formulation form, type of target weeds, application time, etc., but generally the compound of the present invention is 0.1 per 1 are. ~ 40g, preferably 0.5-20
Apply so that it becomes g.

Further, the herbicide of the present invention can be mixed or used in combination with other pesticides, fertilizers, phytotoxicity-reducing agents and the like, and in this case, more excellent effects and actions may be exhibited. For example, when mixed or used in combination with one or more of the following other active ingredients of weeds, a synergistic effect may be exhibited.

2,4,6-trichlorophenyl-4-
Nitrophenyl ether (generic name: chloronitrophen; Chlornitrofen), 5- (2,4-dichlorophenoxy) -2-nitroanisole (generic name: clomethoxyphen; Chrome)
thoxyphen), 2,4-dichlorophenyl-3-carbomethoxy-4
-Nitrophenyl ether (generic name: Bifenox;
biphenylox) and other diphenyl ether compounds,

5-t-butyl-3- (2,4-dichloro-5-isopropoxyphenyl) -1,3,4-oxadiazolin-2-one (generic name: oxadiazone; o
xadiazon), 3N- (2-fluoro-4-chloro-cyclopentyloxyphenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione (Proceedings of the 17th Annual Meeting of the Pesticide Society of Japan, 1992). , Compounds described on page 48), S, S-dimethyl 2-difluoromethyl-4- (2
-Methylpropyl) -6- (trifluoromethyl)-
3,5-Pyridine thioate (generic name: dithiopyr; d
ithiopyr), exo-1-methyl-4- (1-methylethyl) -2
-[(2-Methylphenyl) methoxy] -7-oxabicyclo [2,2,1] heptane (generic name: cinmethylyl), 3,7-dichloroquinoline-8-carboxylic acid (generic name: quinchlorac) Quinclorac), 1- (diethylcarbamoyl) -3- (2,4,6-)
Trimethylphenylsulfonyl) -1,2,4-triazole (Weeds Research, 1991, Vol. 36, No. I, No. 3)
Compounds described in 0th Lecture Lecture Summary, page 27) 3-isopropyl-2,1,3-benzothiadiazin-4-one-2,2-dioxide (generic name: bendazone; bentazone) and its Sodium salt, 2,3-dihydro-3,3-dimethylbenzofuran-
Heterocyclic compounds such as S-ylethanesulfonate (generic name: benfurestate),

2-chloro-2 ', 6'-diethyl-N
-(2-propoxyethyl) acetanilide (generic name:
Pretilachlor; Pretilachlor), α-chloro-N- (3-methoxy-2-thienyl) methyl-2 ′, 6′-dimethylacetanilide (weed research 1989, 34, 2, 131-137. Compound), 2 ', 3'-dichloro-4-ethoxymethoxybenzanilide (chemical regulation of plants, 1983, vol. 18, 2)
No., 151-160) 2-benzothiazol-2-yloxy-N-methylacetanilide (generic name: mefenacet; mefen
acet) α- (2-naphthoxy) propionanilide (generic name: naproanilide), 2- (2,4-dichloro-3-methylphenoxy) propionanilide (generic name: clomeprop;
anilide compounds such as eprop),

S- (4-chlorobenzyl) -N, N-
Diethyl thiocarbamate (generic name: thiobencarb;
Thiobencarb, S-ethylhexahydro-1H-azepine-1-carbothioate (generic name: molinate; molinat)
e),-S-1-methyl-1-phenylethylpiperidine-1
-Carbothioate (generic name: dimepiperate; dim
epiperate), S-benzyl-N- (1,2-dimethylpropyl)-
N-ethyl thiocarbamate (generic name: esprocarb), O-3-t-butylphenyl N- (6-methoxy-
Carbamate compounds such as 2-pyridyl) -N-methylthiocarbamate (generic name: pyributycarb);

A phenoxyalkanoic acid compound such as (R) methyl 2- [4- (4-cyano-2-fluorophenoxy) phenoxy] propionate (a compound described in JP-A-64-66156); -[[(4,6-Dimethoxypyrimidin-2-yl) aminocarbonyl] aminosulfonylmethyl] benzoic acid methyl ester (generic name: bensulfuron-methyl; Bensulfuron-methyl), N-[(4,6-dimethoxy Pyrimidin-2-yl)
Aminocarbonyl] -4-ethoxycarbonyl-1-methyl-5-pyrazolesulfonamide (generic name: pyrazosulfuron-ethyl; pyrazosulfuron-
Ethyl), 1- (2-chloroimidazo [1,2-a] pyridine-
3-ylsulfonyl) -3- (4,6-dimethoxy-2
-Pyrimidinyl) urea (generic name: imazosulfuron), 3- (4,6-dimethoxy-1,3,5-triazin-2-yl) -1- [2- (2-methoxyethoxy)-
Phenylsulfonyl] urea (generic name: cinosulfuron), N-[(4,6-dimethoxypyrimidin-2-yl)
Aminocarbonyl] -3-methyl-5- (2,2-difluoro-2-chloroethoxy) -4-isothiazolesulfonamide (compound described in JP-A-63-190887), and other sulfonylurea compounds,

2- [4- (2,4-dichlorobenzoyl) -1,3-dimethylpyrazol-5-yloxy]
Acetophenone (generic name: pyrazoxifene; pyra
4- (2,4-dichlorobenzoyl) -1,3-dimethyl-5, pyrazolyl-p-toluenesulfonate (generic name: pyrazolate), 2- [4- (2,4-dichloro) -M-Toluo oil)-
1,3-Dimethylpyrazol-5-yloxy] -4 '
-Methylacetophenone (generic name: benzophenap;
a pyrazole-based compound such as benzofenap),

(RS) -2-Bromo-N- (α, α-
Benzylamide compounds such as dimethylbenzyl) -3,3-dimethylbutyramide (generic name: bromobutide), 1- (α-α-dimethylbenzyl) -3- (p-tolyl) urea (generic name: Urea, such as 1- (2-chlorobenzyl) -3- (α, α-dimethylbenzyl) urea (compounds described on the 98th Annual Meeting of the Plant Chemoregulatory Society Research Conference, page 98) Compounds,

2-methylthio-4,6-bis- (methylamino) -s-triazine (general name: cimetrin; s
Imetryn), 2-methylthio-4-ethylamino-6- (1 ',
2'-Diethylpropylamino) -s-triazine (generic name: dimethamethrin)
Triazine compounds, such as

2,4-dichlorophenoxyacetic acid, its salts and esters (generic name: 2,4-di; 2,4-
D), 4- (4-chloro-o-tolyloxy) butyric acid, its salts and esters (generic name: MCPE; MCPB), 5-ethyl 4-chloro-2-methylphenoxythioacetate (generic name) : MCP-thioethyl; M
CPA-thioethyl) and other phenyloxy compounds

[0050]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited thereto. First, specific synthetic examples of the compound of the present invention will be described.

Synthesis Example 1 Synthesis of 1- [1- (benzothiazol-2-yl) -1-methylethyl] -4-methyl-3-phenyl-3-pyrrolin-2-one (Compound No. 11 described below) (1) 5.1 g of sodium hydride was added to 200 ml of dried tetrahydrofuran and cooled to -10 to 0 ° C.
Sodium hydride was suspended. A solution of 10 g of benzothiazol-2-ylacetonitrile dissolved in 50 ml of tetrahydrofuran was added dropwise thereto at 0 to 10 ° C.
After stirring at 70 ° C for 1 hour, the mixture was cooled to -10 to 0 ° C. Then, 17.26 g of iodomethane was added dropwise at −10 to + 10 ° C., and the mixture was reacted at room temperature for 2 nights with stirring.

After completion of the reaction, the reaction product was poured into ice water,
It was extracted with ethyl acetate. Then, it was washed with saline, dried over Glauber's salt, and filtered. The solvent of the obtained filtrate was distilled off under reduced pressure,
Purified by column chromatography (developing solvent: toluene) to give 2- (benzothiazole-) having a melting point of 44 to 46 ° C.
2-yl) -2-methylpropionnitrile 10.75
g was obtained.

(2) 2- (Benzothiazol-2-yl) -2-methylpropionitrile (10.25 g) was added to te.
It was dissolved in 70 ml of rt-butanol, 5.7 g of potassium hydroxide was added thereto, and the mixture was reacted at 80 ° C. for 1 hour with stirring.

After completion of the reaction, the temperature was returned to room temperature, the reaction product was put into water and extracted with ethyl acetate. Then, it was washed with a saline solution and dried with Glauber's salt, and the solvent was distilled off under reduced pressure. The precipitated crystals were washed with a mixed solution of ether: hexane = 1: 1 and dried under reduced pressure to obtain 5.09 g of 2- (benzothiazol-2-yl) -2-methylpropionamide having a melting point of 133 to 134 ° C. .

(3) An aqueous solution prepared by dissolving 2.21 g of sodium hydroxide in 13 ml of water was cooled to -10 to 0 ° C,
Bromine (469 μl) was added dropwise, and the mixture was stirred for 30 minutes. There 2
2 g of-(benzothiazol-2-yl) -2-methylpropionamide was added, and the mixture was reacted at -10 to 0 ° C for 2.5 hours with stirring, and further at room temperature overnight with stirring.

After completion of the reaction, the reaction product has a temperature of -10 to +20.
Hydrochloric acid was added dropwise at 0 ° C to adjust the pH to 1. Then, toluene was added and back extraction was performed with diluted hydrochloric acid (10%), and ammonia was added dropwise to the obtained aqueous layer at -10 to + 20 ° C to adjust the pH to 1
Adjusted to 4. It was extracted with methylene chloride and washed with brine. After that, it was dried over sodium sulfate and the solvent was distilled off under reduced pressure to obtain 870 mg of oily 1- (benzothiazol-2-yl) -1-methylethylamine.

(4) 870 mg of 1- (benzothiazol-2-yl) -1-methylethylamine was dissolved in 20 ml of N, N-dimethylacetamide, and 1.261 ml of triethylamine was added thereto. Then, 721 μl of chloroacetone was added dropwise, and the mixture was reacted at 80 ° C. for 3 hours with stirring. Further, 630 μl of triethylamine and 360 μl of chloroacetone were added, and the mixture was reacted at 80 ° C. for 1 hour with stirring.

After completion of the reaction, the temperature was returned to room temperature, the reaction product was poured into ice water and extracted with ethyl acetate. Then, it was washed with brine and dried over sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 1.17 g of oily [1- (benzothiazol-2-yl) -1-methylethylamino] -2-propanone. .

(5) 1- [1- (benzothiazole-
1.17 g of 2-yl) -1-methylethylamino] -2-propanone was dissolved in 50 ml of dry acetone, 1 g of potassium carbonate was added thereto, and then 966 μl of phenylacetyl chloride was added dropwise at -10 to 0 ° C. The reaction was carried out at room temperature overnight with stirring.

After completion of the reaction, the reaction product was poured into ice water,
It was extracted with ethyl acetate. After that, the extract was washed with a saline solution and dried with sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by column chromatography (developing solvent: methylene chloride) to give oily N- [1- (benzothiazol-2-yl).
1.02 g of -1-methylethyl] -N- (2-oxopropyl) phenylacetamide was obtained.

(6) N- [1- (benzothiazole-
2-yl) -1-methylethyl] -N- (2-oxopropyl) phenylacetamide (6.28 g) was dissolved in ethanol (20 ml), and sodium hydroxide was added thereto (688 m).
g was added, and the mixture was reacted at 80 ° C. for 5 minutes.

After completion of the reaction, the reaction product was poured into ice water,
The pH was adjusted to 4 with hydrochloric acid at -10 to + 10 ° C.
Then, it was extracted with dichloromethane, washed with water, and dried with Glauber's salt. After that, the solvent was distilled off, and the obtained residue was purified by column chromatography (developing solvent: methylene chloride) to obtain 4.47 g of the desired product having a melting point of 152-153 ° C.

Synthesis Example 2 1- [1- (4-chlorobenzothiazol-2-yl)
-1-Methylethyl] -4-methyl-3-phenyl-3
-Synthesis of Pyrrolin-2-one (Compound No. 12 described later) (1) 9.0 g of 4-chlorobenzothiazole was dissolved in 100 ml of ethanol, and hydrazine hydrate 10 was added thereto.
0 ml was added, and the mixture was reacted at reflux temperature for 16 hours.

After completion of the reaction, the solvent was distilled off under reduced pressure to give an oily 2
8.0 g of -amino-3-chlorothiophenol was obtained.

(2) 8.0 g of 2-amino-3-chlorothiophenol was dissolved in 150 ml of ethanol, 200 ml of acetic acid was added to this solution, and then malononitrile was added to 4.
0g was added and it was made to react at room temperature for 3 hours.

After completion of the reaction, the reaction product was poured into water and the precipitated crystals were filtered. After that, it is thoroughly washed with water and dried to give (4-chlorobenzothiazole-
8.0 g of 2-yl) acetonitrile was obtained.

(3) (4-chlorobenzothiazole-
2-yl) acetonitrile 8.0 g was dissolved in tetrahydrofuran 100 ml, and 60% sodium hydride 3.4 g was gradually added to this solution, and then methyl iodide 12 was added.
g was added dropwise, and the mixture was reacted at room temperature for 16 hours.

After completion of the reaction, the reaction product was poured into water, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue is purified by column chromatography (developing solvent: ethyl acetate / hexane = 1/3) to give 2- (4-chlorobenzothiazol-2-yl) -2-methylpro of melting point 95-97 ° C. 6.5 g of pionitrile was obtained.

(4) 6.5 g of 2- (4-chlorobenzothiazol-2-yl) -2-methylpropionitrile
Was dissolved in 80 ml of formic acid, and the solution was reacted at 40 to 50 ° C. for 5 hours while introducing hydrogen chloride gas.

After completion of the reaction, the reaction mixture was poured into water, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue is purified by column chromatography (developing solvent: ethyl acetate / hexane = 1/1) to give 2- (4-chlorobenzothiazol-2-yl) -2-methylpropione having a melting point of 92 to 94 ° C. 6.5 g of amide was obtained.

(5) Sodium hydroxide (4.7 g) was added to water (6).
1.2 ml of bromine was added to an aqueous solution dissolved in 0 ml of -10 to -10.
The mixture was gradually added at 0 ° C. and reacted for 30 minutes. 2- (4-chlorobenzothiazol-2-yl) was added to the obtained reaction solution.
2-Methylpropionamide (6.0 g) was added, and the mixture was reacted at room temperature for 1 hour and further at 80 ° C. for 1 hour.

After completion of the reaction, the reaction product was poured into water, extracted with methylene chloride, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to give oily 1- (4-chlorobenzothiazol-2-yl). ) -1-Methylethylamine 3.6 g
Got

(6) 1- (4-Chlorobenzothiazol-2-yl) -1-methylethylamine (3.5 g), chloroacetone (1.6 g) and triethylamine (1.8 g) were dissolved in tetrahydrofuran (50 ml) and the reflux temperature was adjusted to 1
The reaction was carried out for 6 hours.

After completion of the reaction, the reaction product was poured into water, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by column chromatography (developing solvent: ethyl acetate / hexane = 1/2) to give oily 1- [1- (4-chlorobenzothiazol-2-yl) -1-methylethylamino. ] -2-Propanone (0.9 g) was obtained.

(7) 1- [1- (4-chlorobenzothiazol-2-yl) -1-methylethylamino] -2
-Dissolve 0.9 g of propanone in 20 ml of acetone,
0.48 g of potassium carbonate and 0.54 g of phenylacetyl chloride were added thereto, and the mixture was reacted at room temperature for 16 hours.

After the reaction was completed, the reaction product was poured into water, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue is purified by column chromatography (developing solvent: ethyl acetate / hexane = 1/1) to give N- [1- (4-chlorobenzothiazol-2-yl) -1 having a melting point of 125-127 ° C. 0.6 g of -methylethyl] -N- (2-oxopropyl) phenylacetamide was obtained.

(8) N- [1- (4-chlorobenzothiazol-2-yl) -1-methylethyl] -N- (2
0.6 g of -oxopropyl) phenylacetamide was dissolved in 20 ml of ethanol, 0.08 g of potassium hydroxide was added thereto, and the mixture was reacted at a reflux temperature for 30 minutes.

After completion of the reaction, the reaction product was poured into water, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by column chromatography (developing solvent: ethyl acetate / hexane = 1/1) to obtain 0.1 g of the desired product having a melting point of 63 to 65 ° C.

Synthesis Example 3 1- [1- (6-methoxybenzothiazol-2-yl) -1-methylethyl] -4-methyl-3-phenyl-3-pyrrolin-2-one (Compound No. 15 described later) (1) 2-Cyano-6-methoxybenzothiazole 3
g was dissolved in 100 ml of toluene, and 3 mol /
16 ml of 1-methylmagnesium bromide ether was added, and the mixture was reacted overnight at reflux temperature. Then return to room temperature, add 10 ml of absolute ethanol to react further,
The precipitated crystals were filtered.

Thereafter, the solvent of the filtrate was distilled off, water was added and the mixture was extracted with ethyl acetate and dried over sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue is purified by column chromatography (developing solvent: ethyl acetate) to give an oily 1-
0.5 g of (6-methoxybenzothiazol-2-yl) -1-methylethylamine was obtained.

(2) 0.5 g of 1- (6-methoxybenzothiazol-2-yl) -1-methylethylamine,
Chloroacetone 0.25g and triethylamine 0.2
6 g was dissolved in 20 ml of tetrahydrofuran, and reacted at reflux temperature for 24 hours.

After completion of the reaction, the solvent was distilled off from the reaction product under reduced pressure, and the resulting residue was purified by column chromatography (developing solvent: ethyl acetate / methylene chloride = 1/1) to give an oily 1- [ 0.3 g of 1- (6-methoxybenzothiazol-2-yl) -1-methylethylamino] -2-propanone was obtained.

(3) 1- [1- (6-methoxybenzothiazol-2-yl) -1-methylethylamino]-
2-Propanone (0.3 g) was dissolved in acetone (20 ml), potassium carbonate (0.18 g) and phenylacetyl chloride (0.18 g) were added, and the mixture was reacted at room temperature overnight.

After completion of the reaction, the solvent was distilled off from the reaction product, water was added and the mixture was extracted with ethyl acetate. Then, it was dried over sodium sulfate and the solvent was distilled off under reduced pressure. The obtained residue is subjected to column chromatography (developing solvent: ethyl acetate /
Purified with methylene chloride = 1/1) to give oily N- [1-
0.2 g of (6-methoxybenzothiazol-2-yl) -1-methylethyl] -N- (2-oxopropyl) phenylacetamide was obtained.

(4) N- [1- (6-methoxybenzothiazol-2-yl) -1-methylethyl] -N-
0.2 g of (2-oxopropyl) phenylacetamide
Was dissolved in 20 ml of ethanol, 0.01 g of sodium hydroxide was added thereto, and the mixture was reacted at reflux temperature for 10 minutes.

After completion of the reaction, the solvent was distilled off from the reaction product, water was added and the mixture was extracted with ethyl acetate. Then, it dried with sodium sulfate and the solvent was depressurizingly distilled. The obtained residue was purified by column chromatography (developing solvent: methylene chloride) to obtain 0.1 g of the desired product as an oil.

Next, typical examples of the intermediate compounds of the present invention represented by the above general formulas (II) to (VII) are shown in Tables 1-1 to 1-6 and the above general formula (I). Representative examples of the represented compounds of the present invention are listed in Table 2.

[0088]

[Table 1]

[0089]

[Table 2]

[0090]

[Table 3]

[0091]

[Table 4]

[0092]

[Table 5]

[0093]

[Table 6]

[0094]

[Table 7]

[0095]

[Table 8]

[0096]

[Table 9]

[0097]

[Table 10]

[0098]

[Table 11]

[0099]

[Table 12]

[0100]

[Table 13]

[0101]

[Table 14]

[0102]

[Table 15]

Next, test examples of the present invention will be described. Test Example 1 A paddy field soil was filled in a 1 / 10,000a pot, seeds of Novier and firefly were sown, and lightly covered with soil. Then, leave it in the greenhouse at a water depth of 0.5-1 cm, and
After a day, we planted tubers of Urikawa. Another 1/1
In a pot of 10,000a, soil was similarly filled and water was passed to perform progeny sprouting, and two paddy rice seedlings grown in the two-leaf stage the next day were transplanted in twos per pot. After that, the water depth is 3-4c.
at 0.5 leaf stage for Novier and firefly, early leaf stage for Urikawa, and 4 days after transplanting for paddy rice, the compound of the present invention was diluted with water to prepare a water-dispersible powder. The liquid was uniformly dropped with a pipette so that the predetermined effective amount was obtained.

On the 17th to 20th day after the chemical treatment, the growth condition of the plants was visually observed, and the herbicidal effect and phytotoxicity were evaluated based on the following criteria, and the results shown in Table 3 were obtained.

[0105]

[Table 16]

[0106]

[Table 17]

Test Example 2 A 1 / 10,000a pot was filled with paddy soil, seeds of Novier were sown, and lightly covered with soil. Then, it was left to stand in a greenhouse at a water depth of 0.5 to 1 cm, and when the leaf age reached the 2-leaf stage, the water depth was adjusted to 3 to 4 cm, and the compound of the present invention was prepared according to a usual formulation method. A water-dilutable solution of a wettable powder was uniformly added dropwise with a pipette so as to give a predetermined amount of active ingredient.

On the 18th to 22nd days after the chemical treatment, the growth state was visually observed, and the herbicidal effect was evaluated based on the same criteria as in Test Example 1, and the results in Table 4 were obtained.

[0109]

[Table 18]

[0110]

[Table 19]

Next, formulation examples of the present invention will be described. Formulation Example 1 (1) Compound No. 11 4.01 parts by weight (2) Bentonite 30.00 parts by weight (3) Calcium carbonate 61.49 parts by weight (4) Polycarboxylic acid-based special polymer activator 3.0 parts by weight Part (trade name: Toxanone GR-31A; manufactured by Sanyo Kasei Co., Ltd.) (5) 50% aqueous solution of calcium lignin sulfonate (3.00 parts by weight) (trade name: Sun Extract C; manufactured by Sanyo Kokusaku Pulp Co., Ltd.) )

[0112] (1) and (2) and (3) which have been crushed in advance are mixed, and (4), (5) and water are added thereto and mixed,
Extruded and granulated. Then, it was dried and sized to obtain a granule.

Formulation Example 2 (1) Sikrite 78 parts by weight (2) Condensation product of sodium naphthalene sulfonate and water formalin 2 parts by weight (trade name: Laberin S; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) (3) Polyoxyethylene alkylaryl ether sodium sulfate 5 parts by weight Mixture of sodium salt and white carbon (trade name: Solpol 5039; manufactured by Tsukuba Chemical Industry Co., Ltd.) (4) Amorphous silicon dioxide 15 parts by weight (trade name: car) Plex CS-7; Shionogi Pharmaceutical Co., Ltd.)

A mixture of the above components and compound No. 15 and 9 are mixed in a weight ratio of 9: 1 to obtain a wettable powder.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location A01N 43/76 101 8930-4H 43/78 101 8930-4H C07D 403/06 207 8829-4C 405 / 06 207 8829-4C 409/06 207 8829-4C 413/06 207 8829-4C 417/06 207 9051-4C 417/14 207 9051-4C // (C07D 403/06 207: 00 8314-4C 235: 00) 9164-4C (C07D 413/06 207: 00 8314-4C 263: 00) 9283-4C

Claims (4)

[Claims] 1. A compound represented by the general formula (I): A cyclic amide compound represented by. 2. A compound represented by the general formula (H); A compound of the general formula (I) characterized by dehydration condensation of a compound represented by the formula: (In the formula, R ¹ , R ² , R ³ and m are as described above)
A method for producing a cyclic amide compound represented by: 3. A compound represented by the general formula (I): A herbicide containing a cyclic amide compound represented by: 4. A compound represented by the general formula (IV): A compound represented by.