JPH059176A - Tetrahydroquinolin-1-ylcarbonyl chloride derivative and its production - Google Patents

Abstract

PURPOSE:To provide the subject new compounds useful as an intermediate for production of a herbicide. CONSTITUTION:Compounds. of formula I (X is halogen, lower alkyl, nitro, cyano, trifluoromethyl, etc.; (n) is 1-3), e.g. 6-methyl-1(H),2,3,4- tetrahydroquinolin-1-ylcarbonyl chloride. In addition, the compounds of formula I can be obtained by reacting a compound of formula II with phosgene or trichloromethylchloroformate in an organic solvent such as hexane.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel tetrahydroquinolin-1-ylcarbonyl chloride derivative which is an intermediate for producing tetrahydroquinolin-1-ylcarbonylimidazole having herbicidal or agricultural / horticultural fungicidal activity and a process for producing the same.

[0002]

2. Description of the Related Art U.S. Pat. No. 3,30, known before the filing date of the present application
No. 8,131 describes tertiary carbamyltriazoles and has insecticidal activity. And in the specification, for example, the formula:

[0003]

[Chemical 4]

The compounds represented by are specifically disclosed.

Further, in the publicly known Japanese Patent Publication No. 43-17748, a 2,4,5-tribromoimidazole derivative is described, which has insecticidal and herbicidal activity. And in the specification, for example, the formula:

[0006]

[Chemical 5]

The compounds represented by are specifically disclosed.

[0008]

The present inventors have succeeded in synthesizing a tetrahydroquinolin-1-ylcarbonylimidazole derivative of the following formula (I).

General formula:

[0010]

[Chemical 6]

In the formula, X is a halogen atom, a lower alkyl group, a nitro group, a cyano group, a trifluoromethyl group, a lower alkoxy group optionally substituted with a halogen atom, or a lower alkylthio optionally substituted with a halogen atom. Group, a lower alkylsulfonyl group, a phenyl group, a phenylthio group optionally substituted with a halogen atom, or at least one substituent selected from the group consisting of a halogen atom, a trifluoromethyl group, a nitro group and a lower alkyl group. Represents an optionally substituted phenoxy group, and n represents 1, 2 or 3, and when n is 2 or 3, a plurality of X's may be the same or different, and further, Two Xs are 7- of the tetrahydroquinoline ring in the formula.
5 to 6 carbon atoms together with the 8th and 8th carbon atoms
Is an external group that may form a saturated or unsaturated hydrocarbon ring of and all X is not a chlorine atom when n is 2 or 3.

The compound of the above general formula (I) can be produced, for example, by the following method. Manufacturing method a):-General formula:

[0013]

[Chemical 7]

Wherein X and n are the same as defined above, and a compound of the formula:

[0015]

[Chemical 8]

A process for producing a compound of the above general formula (I), which comprises reacting with a compound represented by

Production method b):- General formula:

[0018]

[Chemical 9]

In the formula, X and n are the same as defined above, and a compound represented by the formula:

[0020]

[Chemical 10]

A process for producing a compound of the above-mentioned general formula (I), which comprises reacting with an imidazole represented by

The compound of the general formula (I) has excellent activity as an active ingredient of a herbicide or an agricultural / horticultural fungicide. The present invention provides the compound of the general formula (III), which is a production intermediate of the general formula (I), and a method for producing the same.

[0023]

The tetrahydroquinolin-1-ylcarbonyl chloride of the present invention is represented by the following general formula (III).

General formula:

[0025]

[Chemical 11]

In the formula, X is a halogen atom, a lower alkyl group, a nitro group, a cyano group, a trifluoromethyl group, a lower alkoxy group optionally substituted with a halogen atom, or a lower alkylthio optionally substituted with a halogen atom. Group, a lower alkylsulfonyl group, a phenyl group, a phenylthio group optionally substituted with a halogen atom, or at least one substituent selected from the group consisting of a halogen atom, a trifluoromethyl group, a nitro group and a lower alkyl group. Represents an optionally substituted phenoxy group, and n represents 1, 2 or 3, and when n is 2 or 3, a plurality of X's may be the same or different, and further, Two Xs are 7- of the tetrahydroquinoline ring in the formula.
5 to 6 carbon atoms together with the 8th and 8th carbon atoms
May form a saturated or unsaturated hydrocarbon ring, provided that when n is 1, X is a group other than a chloro atom and when n is 2 or 3, all X are chloro atoms. Never be.

The compound of the general formula (III) can be produced, for example, by the following method, and the present invention also relates to the above-mentioned production method.

Manufacturing method i):- General formula:

[0029]

[Chemical 12]

In the formula, X and n are the same as defined above, and phosgene or trichloromethylchloroformate is reacted with the compound of the formula (III).

In the above general formula (III), X is a halogen atom, specifically, fluoro, chloro,
Brom and iodo can be exemplified, and as the lower alkyl group,
Specific examples thereof include lower alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, n- (iso-, sec- or tert-) butyl, which are substituted with a halogen atom. As the lower alkoxy group which may be substituted and the lower alkylthio group which may be similarly substituted, specifically, the same carbon numbers 1 to 1 as those exemplified above which may be substituted by the same halogen atom as the above exemplified ones.
The lower alkoxy group and the lower alkylthio group having the lower alkyl group of 4 can be exemplified. Further, as the lower alkylsulfonyl group, specifically, a lower alkylsulfonyl group having a lower alkyl group having 1 to 4 carbon atoms similar to the above examples can be exemplified, and as a phenylthio group which may be substituted with a halogen atom, Specifically, a phenylthio group which may be substituted with a halogen atom similar to the above examples can be exemplified. Further, as the phenoxy group which may be substituted with at least one substituent selected from the group consisting of a halogen atom, a trifluoromethyl group, a nitro group and a lower alkyl group, specifically, the same as the above examples Examples thereof include a phenoxy group which may be substituted with at least one substituent selected from the group consisting of a halogen atom, a trifluoromethyl group, a nitro group and the same lower alkyl group having 1 to 4 carbon atoms as those exemplified above. Furthermore, n is 2 or 3
In the case of, the two Xs together with the 7-position and 8-position carbon atoms of the tetrahydroquinoline ring in the formula form a saturated or unsaturated hydrocarbon ring having 5 to 6 carbon atoms. Alternatively, for example, it may form a benzene ring, a cyclopentane ring, a cyclohexane ring or the like together with the 7-position and 8-position carbon atoms. Then, the general formula (II
The following compounds can be illustrated as a specific example of I).

6-methyl-1 (H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 6
-Ethyl-1 (H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 6-isopropyl-1 (H), 2,3,4-tetrahydroquinoline-1-
Ilcarbonyl chloride, 6-tert-butyl-1
(H), 2,3,4-Tetrahydroquinolin-1-ylcarbonyl chloride, 7-methyl-1 (H), 2
3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 8-methyl-1 (H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 8-
Ethyl-1 (H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 8-propyl-1
(H), 2,3,4-Tetrahydroquinolin-1-ylcarbonyl chloride, 8-fluoro-1 (H), 2
3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 8-bromo-1 (H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 5-
Fluoro-1 (H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 6-fluoro-1
(H), 2,3,4-Tetrahydroquinolin-1-ylcarbonyl chloride, 7-fluoro-1 (H), 2
3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 6-bromo-1 (H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 7-
Bromo-1 (H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 8-iodo-1
(H), 2,3,4-Tetrahydroquinolin-1-ylcarbonyl chloride, 6-nitro-1 (H), 2
3,4-Tetrahydroquinolin-1-ylcarbonyl chloride, 8-nitro-1 (H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 8-
Cyano-1 (H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 8-trifluoromethyl-1 (H), 2,3,4-tetrahydroquinoline-
1-ylcarbonyl chloride, 8-methoxy-1
(H), 2,3,4-Tetrahydroquinolin-1-ylcarbonyl chloride, 6-methoxy-1 (H), 2
3,4-Tetrahydroquinolin-1-ylcarbonyl chloride, 6-isopropoxy-1 (H), 2,3,4
-Tetrahydroquinolin-1-ylcarbonyl chloride, 7-methoxy-1 (H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 7-isopropoxy-1 (H), 2,3,4- Tetrahydroquinolin-1-ylcarbonyl chloride, 8-ethoxy-
1 (H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 6,8-dimethyl-1
(H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 7,8-dimethyl-1 (H),
2,3,4-Tetrahydroquinolin-1-ylcarbonyl chloride, 6,7-dimethyl-1 (H), 2,3
4-tetrahydroquinolin-1-ylcarbonyl chloride, 6,7,8-trimethyl-1 (H), 2,3,4
-Tetrahydroquinolin-1-ylcarbonyl chloride, 6-chloro-8-methyl-1 (H), 2,3,4-
Tetrahydroquinolin-1-ylcarbonyl chloride, 8-chloro-6-methyl-1 (H), 2,3,4-
Tetrahydroquinolin-1-ylcarbonyl chloride, 7-chloro-8-methyl-1 (H), 2,3,4-
Tetrahydroquinolin-1-ylcarbonyl chloride, 6-chloro-8-trifluoromethyl-1 (H),
2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 8-chloro-6-methyl-1 (H),
2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 7-chloro-8-methyl-1 (H),
2,3,4-Tetrahydroquinolin-1-ylcarbonyl chloride, 6-chloro-8-trifluoromethyl-
1 (H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 8-chloro-5-methyl-1
(H), 2,3,4-Tetrahydroquinolin-1-ylcarbonyl chloride, 7-chloro-6-methyl-1
(H), 2,3,4-Tetrahydroquinolin-1-ylcarbonyl chloride, 8-chloro-7-methyl-1
(H), 2,3,4-Tetrahydroquinolin-1-ylcarbonyl chloride, 5-chloro-8-methyl-1
(H), 2,3,4-Tetrahydroquinolin-1-ylcarbonyl chloride, 6-bromo-8-methyl-1
(H), 2,3,4-Tetrahydroquinolin-1-ylcarbonyl chloride, 5-chloro-8-methoxy-1
(H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 6,8-dichloro-5-isopropoxy-1 (H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 6-chloro-8-
Fluoro-5-isopropoxy-1 (H), 2,3,4
-Tetrahydroquinolin-1-ylcarbonyl chloride, 6,8-difluoro-1 (H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride,
7,8-Difluoro-1 (H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 6-trifluoromethyl-1 (H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl Chloride, 7-trifluoromethyl-1 (H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 5-chloro-8-trifluoromethyl-1 (H), 2,3,4-tetrahydro Quinolin-1-ylcarbonyl chloride,
6-chloro-7-trifluoromethyl-1 (H), 2
3,4-Tetrahydroquinolin-1-ylcarbonyl chloride, 7-chloro-8-trifluoromethyl-1
(H), 2,3,4-Tetrahydroquinolin-1-ylcarbonyl chloride, 6,7-difluoro-1
(H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 6,8-dibromo-1 (H),
2,3,4-Tetrahydroquinolin-1-ylcarbonyl chloride, 7,8-dibromo-1 (H), 2,3
4-tetrahydroquinolin-1-ylcarbonyl chloride, 8-chloro-6-fluoro-1 (H), 2,3
4-Tetrahydroquinolin-1-ylcarbonyl chloride, 6-chloro-8-fluoro-1 (H), 2,3
4-Tetrahydroquinolin-1-ylcarbonyl chloride, 8-chloro-7-fluoro-1 (H), 2,3
4-tetrahydroquinolin-1-ylcarbonyl chloride, 6-bromo-8-chloro-1 (H), 2,3,4
-Tetrahydroquinolin-1-ylcarbonyl chloride, 5,6,7-trichloro-1 (H), 2,3,4-
Tetrahydroquinolin-1-ylcarbonyl chloride, 6,7,8-trichloro-1 (H), 2,3,4-
Tetrahydroquinolin-1-ylcarbonyl chloride, 6,7-dimethoxy-1 (H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride,
7,8-dimethoxy-1 (H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 6-methylthio-1 (H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 8-methylthio-
1 (H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 8-ethylthio-1 (H),
2,3,4-Tetrahydroquinolin-1-ylcarbonyl chloride, 6-trifluoromethylthio-1
(H), 2,3,4-Tetrahydroquinolin-1-ylcarbonyl chloride, 8-trifluoromethylthio-
1 (H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 8-chlorodifluoromethylthio-1 (H), 2,3,4-tetrahydroquinoline-
1-ylcarbonyl chloride, 6-trifluoromethoxy-1 (H), 2,3,4-tetrahydroquinoline-
1-ylcarbonyl chloride, 8-trifluoromethoxy-1 (H), 2,3,4-tetrahydroquinoline-
1-ylcarbonyl chloride, 8-difluoromethoxy-1 (H), 2,3,4-tetrahydroquinoline-1
-Ylcarbonyl chloride, 6- (2,6-dichloro-4-trifluoromethylphenoxy) -1 (H),
2,3,4-Tetrahydroquinolin-1-ylcarbonyl chloride, 7-phenoxy-1 (H), 2,3,4
-Tetrahydroquinolin-1-ylcarbonyl chloride, 8- (4-nitrophenoxy) -1 (H), 2
3,4-Tetrahydroquinolin-1-ylcarbonyl chloride, 8- (2,4-dichlorophenoxy) -1
(H), 2,3,4-Tetrahydroquinolin-1-ylcarbonyl chloride, 8- (4-chlorophenylthio) -1 (H), 2,3,4-tetrahydroquinoline-
1-ylcarbonyl chloride, 8-phenyl-1
(H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 8-phenylthio-1 (H),
2,3,4-Tetrahydroquinolin-1-ylcarbonyl chloride, 8- (2-chloro-p-trioxy)-
1 (H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, benzo [h] -1 (H),
2,3,4-Tetrahydroquinolin-1-ylcarbonyl chloride, 8-isopropyl-1 (H), 2,3
4-Tetrahydroquinolin-1-ylcarbonyl chloride, 8-tert-butyl-1 (H), 2,3,4-
Tetrahydroquinolin-1-ylcarbonyl chloride, 8-isopropoxy-1 (H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 7
-Fluoro-8-methyl-1 (H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 8
-Methylsulfonyl-1 (H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride, 7-
(4-trifluoromethylphenoxy) -1 (H),
2,3,4-Tetrahydroquinolin-1-ylcarbonyl chloride, 7,8-trimethylene-1 (H), 2
3,4-tetrahydroquinolin-1-ylcarbonyl chloride, and 7,8-tetramethylene-1 (H),
2,3,4-Tetrahydroquinolin-1-ylcarbonyl chloride.

In the above-mentioned production method, for example, 8-chloro-6-methyl-1 (H), 2,3,4-tetrahydroquinoline and trichloromethyl chloroformate are used and represented by the following reaction formula.

[0034]

[Chemical 13]

The general formula (II of the present invention represented by the above reaction formula
In the method for producing the compound of formula (I), the compound of general formula (I
Specific examples of the compound of I) include 6-methyl-1,2,3,4-tetrahydroquinoline,
6-ethyl-1,2,3,4-tetrahydroquinoline,
6-isopropyl-1,2,3,4-tetrahydroquinoline, 6-tert-butyl-1,2,3,4-tetrahydroquinoline, 7-methyl-1,2,3,4-tetrahydroquinoline, 8-methyl -1,2,3,4-tetrahydroquinoline, 8-ethyl-1,2,3,4-tetrahydroquinoline, 8-propyl-1,2,3,4-tetrahydroquinoline, 8-fluoro-1,2 3,4-tetrahydroquinoline, 8-bromo-1,2,3,4-tetrahydroquinoline, 5-fluoro-1,2,3,4-
Tetrahydroquinoline, 6-fluoro-1,2,3,4
-Tetrahydroquinoline, 7-fluoro-1,2,3
4-tetrahydroquinoline, 6-bromo-1,2,3,
4-tetrahydroquinoline, 7-bromo-1,2,3
4-tetrahydroquinoline, 8-iodo-1,2,3
4-tetrahydroquinoline, 6-nitro-1,2,3,
4-tetrahydroquinoline, 8-nitro-1,2,3
4-tetrahydroquinoline, 8-cyano-1,2,3,
4-tetrahydroquinoline, 8-trifluoromethyl-
1,2,3,4-tetrahydroquinoline, 8-methoxy-1,2,3,4-tetrahydroquinoline, 6-methoxy-1,2,3,4-tetrahydroquinoline, 6-isopropoxy-1,2, 3,4-tetrahydroquinoline,
7-methoxy-1,2,3,4-tetrahydroquinoline, 7-isopropoxy-1,2,3,4-tetrahydroquinoline, 8-ethoxy-1,2,3,4-tetrahydroquinoline, 6,8- Dimethyl-1,2,3,4-tetrahydroquinoline, 7,8-dimethyl-1,2,3
4-tetrahydroquinoline, 6,7-dimethyl-1,
2,3,4-tetrahydroquinoline, 6,7,8-trimethyl-1,2,3,4-tetrahydroquinoline, 6-
Chloro-8-methyl-1,2,3,4-tetrahydroquinoline, 8-chloro-6-methyl-1,2,3,4-tetrahydroquinoline, 7-chloro-8-methyl-1,
2,3,4-tetrahydroquinoline, 6-chloro-8-
Trifluoromethyl-1,2,3,4-tetrahydroquinoline, 8-chloro-5-methyl-1,2,3,4-tetrahydroquinoline, 7-chloro-6-methyl-1,
2,3,4-tetrahydroquinoline, 8-chloro-7-
Methyl-1,2,3,4-tetrahydroquinoline, 5-
Chloro-8-methyl-1,2,3,4-tetrahydroquinoline, 6-bromo-8-methyl-1,2,3,4-tetrahydroquinoline, 5-chloro-8-methoxy-1,
2,3,4-tetrahydroquinoline, 6,8-dichloro-5-isopropoxy-1,2,3,4-tetrahydroquinoline, 6-chloro-8-fluoro-5-isopropoxy-1,2,3, 4-tetrahydroquinoline, 6,8
-Difluoro-1,2,3,4-tetrahydroquinoline, 7,8-difluoro-1,2,3,4-tetrahydroquinoline, 6-trifluoromethyl-1,2,3,4
-Tetrahydroquinoline, 7-trifluoromethyl-
1,2,3,4-tetrahydroquinoline, 5-chloro-
8-trifluoromethyl-1,2,3,4-tetrahydroquinoline, 6-chloro-7-trifluoromethyl-
1,2,3,4-tetrahydroquinoline, 7-chloro-
8-trifluoromethyl-1,2,3,4-tetrahydroquinoline, 6,7-difluoro-1,2,3,4-tetrahydroquinoline, 6,8-dibromo-1,2,3
4-tetrahydroquinoline, 7,8-dibromo-1,
2,3,4-tetrahydroquinoline, 8-chloro-6-
Fluoro-1,2,3,4-tetrahydroquinoline, 6
-Chloro-8-fluoro-1,2,3,4-tetrahydroquinoline, 8-chloro-7-fluoro-1,2,3
4-tetrahydroquinoline, 6-bromo-8-chloro-
1,2,3,4-tetrahydroquinoline, 5,6,7-
Trichloro-1,2,3,4-tetrahydroquinoline,
6,7,8-Trichloro-1,2,3,4-tetrahydroquinoline, 6,7-dimethoxy-1,2,3,4-tetrahydroquinoline, 7,8-dimethoxy-1,2,
3,4-tetrahydroquinoline, 6-methylthio-1,
2,3,4-tetrahydroquinoline, 8-methylthio-
1,2,3,4-tetrahydroquinoline, 8-ethylthio-1,2,3,4-tetrahydroquinoline, 6-trifluoromethylthio-1,2,3,4-tetrahydroquinoline, 8-trifluoromethylthio-1 , 2, 3, 4
-Tetrahydroquinoline, 8-chlorodifluoromethylthio-1,2,3,4-tetrahydroquinoline, 6-trifluoromethoxy-1,2,3,4-tetrahydroquinoline, 8-trifluoromethoxy-1,2,3, 4-
Tetrahydroquinoline, 8-difluoromethoxy-1,
2,3,4-tetrahydroquinoline, 6- (2,6-dichloro-4-trifluoromethylphenoxy) -1,
2,3,4-tetrahydroquinoline, 7-phenoxy-
1,2,3,4-tetrahydroquinoline, 8- (4-nitrophenoxy) -1,2,3,4-tetrahydroquinoline, 8- (2,4-dichlorophenoxy) -1,2,
3,4-tetrahydroquinoline, 8- (4-chlorophenylthio) -1,2,3,4-tetrahydroquinoline,
8-phenyl-1,2,3,4-tetrahydroquinoline, 8-phenylthio-1,2,3,4-tetrahydroquinoline, 8- (2-chloro-p-trioxy) -1,
2,3,4-tetrahydroquinoline, benzo [h]-
1,2,3,4-tetrahydroquinoline, 8-isopropyl-1,2,3,4-tetrahydroquinoline, 8-t
ert-butyl-1,2,3,4-tetrahydroquinoline, 8-isopropoxy-1,2,3,4-tetrahydroquinoline, 7-fluoro-8-methyl-1,2,3,
4-tetrahydroquinoline, 8-methylsulfonyl-
1,2,3,4-tetrahydroquinoline, 7- (4-trifluoromethylphenoxy) -1,2,3,4-tetrahydroquinoline, 7,8-trimethylene-1,2,
Examples thereof include 3,4-tetrahydroquinoline and 7,8-tetramethylene-1,2,3,4-tetrahydroquinoline.

The above-mentioned process for producing the compound of the general formula (III) of the present invention can be carried out using a solvent or a diluent. For this purpose, all inert solvents and diluents can be used.

Examples of the solvent or diluent include aliphatic cycloaliphatic and aromatic hydrocarbons (which may be optionally chlorinated), for example, hexane, cyclohexane,
Petroleum ether, ligroin, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, ethylene chloride and tri-chloroethylene,
Chlorbenzene; Other ethers such as diethyl ether, methyl ethyl ether, di-iso-propyl ether, dibutyl ether, propylene oxide, dioxane, tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl-iso-propyl ketone, methyl-iso. -Butyl ketone; Nitriles such as acetonitrile, propionitrile, acrylonitrile; Esters such as ethyl acetate, amyl acetate; Acid amides such as dimethylformamide, dimethylacetamide; Sulfones, sulfoxides such as dimethyl sulfoxide, sulfolane; and bases such as ,
Pyridine and the like can be mentioned.

The above method can be carried out within a wide temperature range. For example, it can be carried out between -20 ° C and the boiling point of the mixture, preferably between 0 and 100 ° C. The reaction is preferably carried out under normal pressure, but it is also possible to operate under increased pressure or reduced pressure.

The compound of the present invention, which is produced by using the compound of the general formula (III) as a production intermediate, has low toxicity to warm-blooded animals and has good selectivity to cultivated plants. That is, since it has a characteristic that the cultivated plant is not harmful to the cultivated plant at a usual use concentration, it can be conveniently used for controlling weeds, for example, as a herbicide. And the herbicide of the present invention is particularly a pre-emergence soil treatment agent for paddy weeds,
When used as a foliar and soil treatment agent, it exhibits excellent selective control efficacy.

As described above, the compound of the general formula (I) is excellent in safety and exhibits an excellent herbicidal effect.

The compound of the general formula (I) is excellent in safety, exhibits excellent herbicidal activity, and has a broad herbicidal spectrum.

For example, as paddy field weeds, the plant name Latin name dicotyledonous plant Rotala indica Koehne Azena Lindernia Procumbens Phi-lcox Coptia de Ludwigia prostrata rot rog rota rog rot rog rot rog roth rog rot rot rog rota rog rota rog rota rog rot rot rog rot roth rot rot rog roth roth roth roth rot roth rot roth roth roth roth roth roth rot roth rot roth rot roth rot rot rot roth roth roth roth roth roth roth roth roth roth roth roth roth roth roth rota Benn Echinochloa crus-galli P Beauv. Echinochloa crus Elatin triandra Schk monocot var. Konagi Monochoria vaginalis Pre-sl pine by Eleocharis acicularis L. Kurogui Eleocharis Kuroguwai Okwi Cyperus difformis L. Cyperus serotonus Rottbo-el Urikawa Sagittaria pygmaea Miq Hera modaka Alisma caniculatum A. Br. et Bouche Firefly Sirpus juncoides Roxbur- gh var. And the like have a herbicidal activity, and have no harmful effect on rice.

As the field weeds, for example,    Plant name latin name Dicotyledon   Polygonum sp.   Akaza Chenopodium album Linnae-                       us   Chickweed Stellaria media Villas   Portulaca Portulaca oleracea Linna-                       eus. Monocot   Echinochloa crus-galli P.                       Beauv.   Mexicana Digitaria adscendens Henr                       ．   Cyperus cyperus iria L. Etc. have herbicidal activity.

However, the types of plants described above are typical examples of the genus listed by the Latin name.

However, the adaptability of the compound of the general formula (I) is not limited only to paddy fields and upland weeds, but to weeds harmful to grasses and weeds such as fallow land. However, it is effective. The word weed here is
In the broadest sense, it means any plant that grows in undesirable places.

Further, the compound of the general formula (I) has a strong bactericidal activity against a wide variety of plant pathogens, and has an excellent residual effect, so that it can be applied to the control of plant diseases.

The bactericidal spectrum is, for example, Archaebacteria [Archimycetes], Algae [Phycomycetes], Ascomycetes [Ascomycetes], Basidiomycetes [Basidiomycetes]
s)], incomplete bacterium [Hungi Im Perfecty (Fu
ngi Imperfecti)] and other various plant diseases caused by bacteria.

Specific examples of useful bactericidal spectra of the compound of the general formula (I) include, for example, rice blast (P).
yricularia oryzae), rice sesame leaf blight (Ophibolus miyabebnus), black spot of cruciform plant (Alternaria brass)
icae), apple leaf spot disease (Alternari)
a mali), Black spot of pear (Alternaria)
kukuchiana), scab of various crops (Phyt
ophthora infestans), anthracnose of cucumber (Colletotrichum lagenar)
ium) and the like, and is important as a bacterial disease (Xanthomonas oryz)
Ae) can also be mentioned.

When the compound of the general formula (I) is used as a herbicide or a fungicide for agricultural and horticultural use, various preparations can be prepared by a method generally used in the field of agricultural chemicals production using an agricultural chemical auxiliary. It can be used in the form. In actual use, these various formulations can be used directly as they are or diluted with water to a desired concentration and used.

Examples of the agricultural chemicals adjuvants mentioned here include diluents (solvents, extenders, carriers), surfactants (solubilizers, emulsifiers, dispersants, wetting agents), stabilizers, fixing agents, aerosols. Examples include propellants and synergists.

As the solvent, water: organic solvent; hydrocarbons [eg, n-hexane, petroleum ether, naphtha, petroleum fraction (paraffin wax, kerosene, light oil, middle oil, heavy oil), benzene, toluene, xylenes] , Halogenated hydrocarbons [eg, chloromethylene, carbon tetrachloride, trichloroethylene, ethylene chloride, ethylene dibromide, chlorobenzene, chloroform], alcohols [eg, methyl alcohol, ethyl alcohol, propyl alcohol, ethylene glycol], ether [Eg ethyl ether, ethylene oxide, dioxane], alcohol ethers [eg ethylene glycol, monomethyl ether], ketones [eg acetone, isophorone], esters [eg ethyl acetate, amyl acetate],
Examples thereof include amides [eg, dimethylformamide, dimethylacetamide] and sulfoxides [eg, dimethylsulfoxide].

Inorganic powder or granules as a bulking agent or carrier;
Slaked lime, magnesium lime, gypsum, calcium carbonate, silica, perlite, pumice, calcite, diatomaceous earth, amorphous silicon oxide, alumina, zeolite, clay minerals (e.g., baylophyllite, talc, montmorillonite, pyderite, permiculite, kaolinite, mica) ): Vegetable powder; cereal flour, starch, modified starch, sugar, glucose,
Plant stem trunk crushed product: synthetic resin powder and granules; phenol resin, urea resin, vinyl chloride resin can be mentioned. As the surfactant, anionic (anion) surfactant; alkyl sulfates [eg sodium lauryl sulfate], aryl sulfonic acids [eg alkyl aryl sulfonate, sodium alkyl naphthalene sulfonate], succinates, polyethylene glycol Alkyl aryl ether sulfate ester salts: cationic (cationic) surfactants; alkyl amines [eg, lauryl amine, stearyl trimethyl ammonium chloride, alkyl dimethyl benzyl ammonium chloride], polyoxyethylene alkyl amines: nonionic surfactants; Polyoxyethylene glycol ethers [eg, polyoxyethylene alkylaryl ethers and condensates thereof], polyoxyethylene glycol esters [eg , Polyoxyethylene fatty acid esters, polyhydric alcohol esters [e.g., polyoxyethylene sorbitan monolaurate: amphoteric surfactants, and the like.

In addition, stabilizers, fixing agents [eg agricultural soap, casein lime, sodium alginate, polyvinyl alcohol (pVA), vinyl acetate adhesives, acrylic adhesives], aerosol propellants [eg trichlorofluoro]. Methane, dichlorofluoromethane, 1,2,2
-Trichloro-1,1,2-trifluoroethane, chlorobenzene, LNG, lower ether]: (for smoking agents) combustion regulator [eg nitrite, zinc dust, dicyandiamide]: oxygen supplier [eg chloric acid Salt]: Potency extender:
Dispersion stabilizers [eg casein, tragacanth, carpoxymethylcellulose (CMC), polyvinyl alcohol (pVA)]: Synergists can be mentioned.

The compound of the general formula (I) can be produced in various dosage forms by a method generally used in the field of agricultural chemicals production. The form of the formulation is emulsion: oil:
Wettable powder: Water solvent: Suspension: Powder: Granules: Powder granules: Smoke: Tablets: Fumes: Pastes: Capsules.

The herbicidal or agricultural / horticultural fungicide of the present invention may contain the above-mentioned active ingredient in an amount of, for example, about 0.001 to 100% by weight, preferably about 0.005 to about 95% by weight. In actual use, the various formulations and spray preparations (ready-to-use-prepa) described above are used.
content of the active compound is, for example, about 0.0
A range of 1 to about 95% by weight, preferably about 0.05 to about 60% by weight is suitable.

The content of these active ingredients can be appropriately changed depending on the form of the preparation, the method of application, the purpose, time, place, weeds, occurrence of plant diseases and the like.

The compound of the general formula (I) of the present invention can be further used, if necessary, with other pesticides such as insecticides, fungicides, acaricides, nematicides, antiviral agents, herbicides and plant growth agents. Modulators, attractants [for example, organic phosphate compounds, carbamate compounds, dithio (or thiol) carbamate compounds, organic chlorine compounds, dinitro compounds,
Organic sulfur or metal-based compounds, antibiotics, substituted diphenyl ether-based compounds, urea-based compounds, triazine-based compounds] or / and fertilizers can also coexist.

Various formulations or spray-ready preparations containing the active ingredients according to the invention (ready-to-use-p)
application is a method generally used in the field of agricultural chemicals production, spraying [for example, liquid agent spraying (spraying), misting (atomizing), dusting, granulation, water surface application,
Pouring: Smoke: Soil application [eg mixing, sprinkling
g), fumigation, irrigation]: surface application [eg, coating, banding, powder coating, coating]: dipping or the like. In addition, the so-called ultra-low-volume small-volume spray method (ultra-low-volume)
It can also be used according to e). In this way it is possible to contain 100% of the active ingredient.

When used as a herbicide, the application rate per unit area is, for example, about 0.1 to about 8 kg, preferably about 0.25 to about 5, as the active compound per hectare.
An application rate of kg can be exemplified. When used as an agricultural and horticultural germicide, the active compound may be used in an amount of, for example, about 1 to about 10 kg per hectare. However, in special cases it is possible, and sometimes even necessary, to exceed or fall below these ranges.

It contains a compound of the above general formula (I) as an active ingredient and contains a diluent (solvent and / or extender and / or carrier) and / or a surfactant, and if necessary, for example a stabilizer, a sticking agent. , A herbicidal or agricultural / horticultural germicidal composition containing a synergist can be provided.

Furthermore, according to the present invention, the compound of the general formula (I) is used alone or in a diluent (solvent and / or extender and / or carrier) at weeds, phytopathogenic fungi and / or where they occur. And / or a surfactant,
Further, if necessary, a method for controlling weeds and plant diseases can be provided in which a stabilizer, a sticking agent, and a synergist are mixed and applied.

Next, the content of the present invention will be specifically described with reference to examples, but the present invention should not be limited to these.

Example 1 A solution of trichloromethyl chloroformate (20 ml) in ethyl acetate (100 ml) was added at 50-60 ° C.
Warm (oil bath temperature) and, with stirring, a solution of 7-chloro-8-methyl-1,2,3,4-tetrahydroquinoline (9 g) in ethyl acetate (20 ml) over 30 minutes,
Drop it. The reaction temperature is then gradually raised to the reflux temperature and stirred for 5 hours. The solvent was distilled off on a steam bath, and the residue was distilled under high vacuum to obtain the desired 7-chloro-8-methyl-1 (H), 2,3,4-tetrahydroquinoline-1- Ilcarbonyl chloride (9.5 g) is obtained. bp. 165-170 ° C /
0.4 mmHg

[0064]

[Chemical 14]

The compounds of the general formula (III) of the present invention synthesized by the same method as in Example 1 are shown in Table 1 below.

[0066]

[Table 1]

[0067]

[Table 2]

[0068]

[Table 3]

[0069]

[Table 4]

[0070]

[Table 5]

Reference Synthesis Example 1 [Synthesis Example of Compound of General Formula (I)] 7-chloro-8-methyl-1,2,3,4-tetrahydroquinoline (1.8 g) and N, N'-carbonyldiimidazole (1.6 g) in toluene (20 ml),
Heat and stir for 24 hours. The solvent is distilled off under reduced pressure, and the residue is further depressurized under vacuum at 1 mmHg at 80 ° C. Water was added to the residue for crystallization, and the crystals were filtered to give the desired 7-chloro-8-methyl-1 (H), 2,3,3 represented by the formula below.
4-Tetrahydroquinolin-1-ylcarbonylimidazole (2.1 g) is obtained. It recrystallizes from ether.

Mp. 115-117 ° C

[0073]

[Chemical 15]

Reference Synthesis Example 2 [Synthesis Example of Compound of General Formula (I)] 7,8-Dimethyl-1 (H), 2,3,4-tetrahydroquinolin-1-ylcarbonyl chloride (2.2
g) and imidazole (2.0 g) are stirred in tetrahydrofuran (20 ml) for 16 hours at reflux temperature. Tetrahydrofuran and excess imidazole are distilled off under reduced pressure. Water was added to the residue for crystallization, and the crystals were filtered to obtain the desired 7,8-dimethyl-1 (H), 2,2 represented by the following formula.
3,4-Tetrahydroquinoline-1-carbonylimidazole (2.2 g) is obtained. It crystallizes from ether.

Mp. 122-124 ° C

[0076]

[Chemical 16]

Compounds of general formula (I) synthesized according to the same method as in Reference Synthesis Example 1 or 2 are shown in Table 2 below.

[0078]

[Table 6]

[0079]

[Table 7]

[0080]

[Table 8]

[0081]

[Table 9]

[0082]

[Table 10]

Reference Example 1 (Wettable powder) Compound No. 1 of formula (I) 1,15 parts, a mixture of powdered diatomaceous earth and powdered clay (1: 5), 80 parts, sodium alkylbenzenesulfonate, 2 parts, sodium alkylnaphthalenesulfonate formalin condensate, 3 parts by pulverization and mixing, and hydration Use as an agent. It is diluted with water and sprayed onto weeds, pathogens and / or their outbreaks.

Reference Example 2 (Emulsion) Compound No. of formula (I) 33, 30 parts, xylene, 55
Part, polyoxyethylene alkyl phenyl ether, 8
And 7 parts of calcium alkylbenzene sulfonate are mixed and stirred to prepare an emulsion. It is diluted with water and sprayed on weeds, pathogens and / or their outbreaks.

Reference Example 3 (powder) Compound No. of formula (I) 3, 2 parts, powdered clay and 98 parts are crushed and mixed to obtain a powder. This is dusted to weeds, pathogens and / or their outbreaks.

Reference Example 4 (powder) Compound No. of formula (I) 2, 1.5 parts, isopropyl hydrogen phosphate (pAP), 0.5 part, powdered clay, 98 parts are pulverized and mixed to give a powder, which is then dusted on weeds, pathogens and / or where they occur.

Reference Example 5 (Granule) Compound No. of formula (I) 1, 10 parts, bentonite (montmorillonite), 30 parts, talc (talc), 58 parts,
Lignin sulfonate, to a mixture of 2 parts, water and 25 parts were added, kneaded well, and mixed with an extrusion type granulator for 10 to 4
Granules of 0 mesh are dried at 40 to 50 ° C to obtain granules. It granulates weeds, pathogens and / or their outbreaks.

Reference Example 6 (Granule) Clay mineral particles having a particle size distribution of 0.2 to 2 mm, 95 parts, were put in a rotary mixer, and the compound No. 1 of the present invention was dissolved in an organic solvent under rotation. After spraying 29 and 5 parts of the mixture to make it uniform, it is dried at 40 to 50 ° C. to give granules. It granulates weeds, pathogens and / or their outbreaks.

Reference Example 7 (Biological test) Submerged understem and soil treatment test for paddy weeds (pot test) Preparation of active compound Carrier: 5 parts by weight of acetone Emulsifier: 1 part by weight of benzyloxypolyglycol ether Preparation of active compound The agent is obtained as an emulsion by mixing 1 part by weight of the active compound with the above-mentioned amounts of the carrier and the emulsifier. It is prepared by diluting a prescribed amount of the preparation with water.

Test method Wagner pots of 1 / 5,000 are were filled with paddy soil and paddy rice seedlings of 2 to 3 leaf stage (plant height: about 10 cm) (variety:
2 seeds per pot were transplanted. Furthermore, Novie,
Cyperaceae, eel, firefly, broad-leaved weed seeds, and pieces of Pinus sylvestris and tubers of Spodoptera litura were inoculated and kept moist. After the Nobye grew around the 2 leaf stage (about 7 to 9 days after inoculation), it was flooded to about 6 cm, and the compound of the present invention was made into an emulsion form and a predetermined amount was treated with a pipette. After processing 1
Leakage treatment for 2 days at a rate of 2-3 cm per day, then about 3
cm watering condition, weeding effect 4 weeks after chemical treatment,
The degree of phytotoxicity was classified and evaluated according to the following criteria on a scale of 0 to 5.

The evaluation of the effect was as follows when compared with the untreated plot. 5: More than 95% of herbicidal rate against untreated area (withered) 4: 〃 80% or more and less than 95% 3: 50% or more and less than 80% 2: 〃 30% or more and less than 50% 1: 〃 10% or more and less than 30% 0: Less than 10% (no effect) Evaluation of phytotoxicity to paddy rice is 5: 95% or more herbicidal rate against untreated area (fatal damage) 4: 50% or more and less than 90% 3: 〃 30% or more and less than 50% 2: 〃 10% or more and less than 30% 1: 〃 0 or less than 10% 0: 〃 0% (no chemical damage) And

The abbreviations of weeds are A, B, C, D, E,
F, G, and H are as follows, respectively.

Table 3 shows the results of the test of A: Taenia cinerea, B: pine nut, C: cyperaceae, D: firefly, E: eel, F: broad-leaved weeds (Azena, Pyrococcus japonicus, Mizochabe, etc.) and G: Cyperus edulis.

[0094]

[Table 11]

Note) Control A-1: US Pat.
No. 8,131 Compound described in the specification

[0096]

[Chemical 17]

B-1: Compounds described in the specification of JP-B-43-17748.

[0098]

[Chemical 18]

Reference Example 8 (Biological test) Foliar spraying efficacy test against rice sesame leaf blight Rice paddy rice (cultivar: Kusabue) was cultivated in a 12 cm diameter biscuit pot, and its 3-4 leaf stage was performed according to Reference Example 1. Then, 50 ml of the prepared diluted solution of the test compound having a predetermined concentration was sprayed per 3 pots.
Next day, a suspension of rice sesame leaf blight fungal spores that had been artificially cultured on the next day was spray-inoculated (twice) and kept in a humid chamber at 25 ° C. and 100% relative humidity for infection. Seven days after the inoculation, the degree of morbidity per pot was classified and evaluated according to the following criteria, and the control value (%) was determined.

[0100] Degree of illness Degree of illness 0 no illness 1 minute 2 small 3 in 4 many 5 Jin

[0101]

[Equation 1]

This test is a result of 3 pots in 1 section. As a result, for example, compound No. Ten compounds showed a control value of 100% at an active ingredient concentration of 500 ppm. Further, the control compounds A-1 and B-1 of the above-mentioned Example 9 were 500 ppm, and the control value was 10% or less. Reference Example 9 (Biological test) Control test against scab of tomato Tomato (cultivar: Kurihara) cultivated in a 9 cm unglazed pot was sprayed with a test compound in emulsion form prepared according to Reference Example 1 using a spray gun. did. One day after spraying, inoculate with a spore suspension of this disease fungus, and
After leaving it in a constant temperature room at ℃ and humidity of 90% or more overnight,
After 5 days, the disease rate was classified and evaluated according to the following criteria by the lesion area ratio, and the control value was obtained.

[0103] Disease rate Lesion area ratio (%) 0 0 0.5 2 or less 1 3-5 26-15 3 16-30 4 31-50 5 51 or more

[0104]

[Equation 2]

As a result, for example, compound No. 7, 1
0, 28 and 34 showed a control value of 100% at an active ingredient concentration of 500 ppm. At the same time, the control values of the above-mentioned control compounds A-1 and B-1 were 0.

Reference Example 10 (Biological test) Foliar spraying efficacy test against rice blast Preparation of test compound Active compound: 50 parts by weight Carrier: Mixture of diatomaceous earth and kaolin (1: 5) 45 parts by weight Emulsifier: polyoxy Ethylene alkyl phenyl ether 5 parts by weight The above-mentioned amounts of the active compound, carrier and emulsifier are ground and mixed to obtain a wettable powder, and a predetermined amount thereof is diluted with water.

Test method Paddy rice (variety: Asahi) was cultivated in a clay pot with a diameter of 12 cm,
In the 3 to 4 leaf stage, 50 ml of a diluted solution of the test compound having a predetermined concentration prepared above was sprayed per 3 pots. Next day, spray-inoculate a suspension of rice blast fungus spores artificially cultured (twice)
Then, they were infected by keeping them in a humid chamber at 25 ° C. and a relative humidity of 100%. Seven days after the inoculation, the degree of morbidity per pot was classified and evaluated according to the following criteria, and the control value (%) was determined. The drug damage was also investigated at the same time.

[0108] Disease rate Lesion area ratio (%) 0 0 0.5 2 or less 1 3-5 26-10 3 11-20 4 21-40 5 41 or more

[0109]

[Equation 3]

As a result, for example, compound No. 10, 22
And 32 compounds showed a control value of 100% at an active ingredient concentration of 500 ppm. The control compounds A-1 and B-1 had a control value of 10% or less at 500 ppm.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Reference number within the agency FI Technical display location C07D 215/26 7019-4C 215/36 7019-4C 215/48 7019-4C 221/10 6701-4C 221/16 6701-4C 401/06 8829-4C // A01N 43/50 J 8930-4H (C07D 401/06 215: 00 233: 00) (C07D 401/06 221: 00 233: 00) (72) Inventor's collection (3) 2-24-10 Higashi-Toyota, Hino-shi, Tokyo (72) Inventor Koichi Moriya 39-15 Namiki-cho, Hachioji-shi, Tokyo (72) Inventor Hidenori Hayakawa 3-3-19 Midori-cho, Musashino-shi, Tokyo

Claims (2)

[Claims] 1. A general formula: In the formula, X is a halogen atom, a lower alkyl group, a nitro group,
A cyano group, a trifluoromethyl group, a lower alkoxy group optionally substituted with a halogen atom, a lower alkylthio group optionally substituted with a halogen atom, a lower thio group,
Or a phenoxy group which may be substituted with at least one substituent selected from the group consisting of a halogen atom, a trifluoromethyl group, a nitro group and a lower alkyl group, and n is 1, 2 or 3 When n is 2 or 3, a plurality of X's may be the same or different, and further, two X's are carbons at the 7-position and 8-position of the tetrahydroquinoline ring in the formula. Together with the atom, it may form a saturated or unsaturated hydrocarbon ring having 5 to 6 carbon atoms, provided that when n is 1, X is a group other than a chloro atom and n is 2 Or in the case of 3, all X are not chloro atoms. 2. A general formula: In the formula, X is a halogen atom, a lower alkyl group, a nitro group,
Cyano group, trifluoromethyl group, lower alkoxy group optionally substituted with halogen atom, lower alkylthio group optionally substituted with halogen atom, lower alkylsulfonyl group, phenyl group, optionally substituted with halogen atom A phenylthio group, or a phenoxy group which may be substituted with at least one substituent selected from the group consisting of a halogen atom, a trifluoromethyl group, a nitro group and a lower alkyl group, and n is 1, 2 or Or 3
, And when n is 2 or 3, multiple X's
May be the same or different, and two Xs together with the carbon atoms at the 7-position and 8-position of the tetrahydroquinoline ring in the formula are saturated or unsaturated having 5 to 6 carbon atoms. May form a hydrocarbon ring, provided that when n is 1, X is a group other than a chloro atom and when n is 2 or 3, all X are not chloro atoms. Characterized by reacting a compound represented by: with phosgene or trichloromethylchloroformate. In the formula, X and n are the same as defined above, and a method for producing the compound represented by: