JP2000159754A - Herbicidal 1,3,5-triazine compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound having higher herbicidal ability and higher safety as well. SOLUTION: This new compound is a compound of formula I [A is CHR3R4 (R3 and R4 are each a 1-6C alkyl, 3-7C cycloalkyl or 1-4C haloalkyl) or the like; R is H, formyl or a 1-3C alkylcarbonyl; R2 is 1-fluoroethyl or 1-fluoro-1- methylethyl], e.g. N-(1-ethylpropyl)-6-(1-fluoro-1-methylethyl)-1,3,5-triazine-2,4- diamine. The compound of formula I (wherein R1 is H) is obtained by reaction of an alkyl biguanide salt of formula II (X1 is a halogen) with a carboxylic ester of the formula R2COOR5 (R5 is a 1-4C alkyl).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to novel 1,3,5-triazines and their use as herbicides.

[0002]

BACKGROUND OF THE INVENTION It is already known that certain 1,3,5-triazines have herbicidal activity (Japanese Patent Publication No. 36-19400, U.S. Pat. No. 3,816,316).
419, U.S. Pat. No. 3,932,167,
JP-A-58-192873, WO 90/093
78 etc.).

[0003] The present inventors have been conducting research for many years to develop excellent herbicides, and in order to create compounds having higher herbicidal ability and higher safety against herbicide. Have synthesized many compounds and studied their herbicidal properties.

[0004]

As a result, novel 1,3,5-triazines represented by the following general formula (I) have now been found.

[0005]

Embedded image In the formula, A is CHR ³ R ⁴ (where R ³ and R ⁴ are the same or different and each represent C _1-6 alkyl, C _3-7 cycloalkyl or C _1-4 haloalkyl, provided that R ³ and R total carbon number of ⁴ is 4 or more), C ₁ haloalkyl substituted C _3-6 cycloalkyl, C _3-6 alkynyl or C _1-4
Represents a cyanoalkyl, R ¹ represents a hydrogen atom, formyl or C _1-3 alkylcarbonyl, and R ² represents 1-fluoroethyl or 1-fluoro-1-methylethyl.

The compound of the formula (I) of the present invention can be produced, for example, by the following production methods (a), (b), (c), (d) or (e). Production method (a): when R ¹ represents a hydrogen atom, the formula

[0007]

Embedded image Wherein A is as defined above, and X ¹ represents a halogen atom, and a salt of an alkyl biguanide represented by the formula: R ² COOR ⁵ (III) wherein R ² is as defined above; ⁵ represents a C _1-4 alkyl, a method of reacting with a carboxylic acid ester represented by the formula: Production method (b): Formula

[0008]

Embedded image Wherein A and R ² have the same meaning as described above, and a compound represented by the formula R ¹ X ² (IV), wherein R ¹ has the same meaning as described above, and X ² represents chlorine or bromine. A method of reacting with the represented carboxylic acid halide. Production method (c): A method of reacting the compound of the formula (Ia) with a carboxylic anhydride represented by the formula R ¹ OR ¹ (V) wherein R ¹ has the same meaning as described above. Production method (d): a method of reacting the compound of the formula (Ia) with a carboxylic acid ester represented by the formula: R ¹ OR ⁵ (VI) wherein R ¹ and R ⁵ have the same meanings as described above. Production method (e): A method of reacting the compound of the formula (Ia) with a carboxylic acid represented by the formula: R ¹ OH (VII), wherein R ¹ and R ⁵ are as defined above.

The compounds of the formula (I) according to the invention have a strong herbicidal action and are, surprisingly, very outstanding compared to, for example, the known compounds described in the prior art mentioned above. Shows herbicidal action.

In the present specification, "halogen" represents fluoro, chloro, bromo or iodo, preferably fluor, chloro or bromo.

"Alkyl" can be linear or branched, and includes, for example, C _1-6 alkyl, specifically, methyl, ethyl, n-propyl, i-alkyl.
Propyl, n-, i-, sec- or tert-butyl, n-, i-, sec-, tert- or ne
Examples thereof include o-pentyl, n-, i-, sec-, tert- and neo-hexyl.

"Alkynyl" may be linear or branched and includes, for example, C _2-6 alkynyl, and specifically, ethynyl, 1-propynyl, 2-
Examples thereof include propynyl, 1-methyl-2-propynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl and the like.

"Cycloalkyl" optionally includes, for example, halogen (fluoro, chloro, bromo or iodo),
C _1-4 alkyl (methyl, ethyl, n-propyl, i-
C _3-7 which may be substituted by
Cycloalkyl; specifically, cyclopropyl, 2-methylcyclopropyl, 2-chloro-cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2-fluorocyclopentyl, cyclohexyl, 4-methylcyclohexyl, Examples thereof include fluorocyclohexyl and cycloheptyl.

"Haloalkyl" refers to a halogen-substituted linear or branched alkyl, for example, C 1 -C 3 substituted by fluoro, chloro or bromo.
_1-4 alkyl can be mentioned, specifically, fluoromethyl, trifluoromethyl, 2-fluoroethyl,
Examples thereof include 2-chloroethyl, 2-bromoethyl, 2,2,2-trifluoroethyl, 1-fluoroethyl, 3-fluoropropyl, and 3-chloropropyl.

The alkyl part of “cyanoalkyl” and “alkylcarbonyl” has the same meaning as the above “alkyl”, and specific examples of “cyanoalkyl” include cyanomethyl, 1-cyanoethyl, 2-cyanoethyl, 3
-Cyanopropyl, 1-cyanopropyl, 1-cyano-
Examples thereof include 1-methylethyl and 4-cyanobutyl, and specific examples of “alkylcarbonyl” include methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, i-propylcarbonyl, n-butylcarbonyl and the like. be able to.

A preferred group of compounds of the present invention include compounds of the formula
In (I), A is CHR^ThreeR^Four(Where R^ThreeAnd R^Four
Are the same or different and each is C_{1- Five}Alkyl, C
_3-6Cycloalkyl or C_1-3Represents haloalkyl, provided that
Then R^ThreeAnd R ^FourHas a total carbon number of 4 or more), C₁Halo
Alkyl-substituted C_5-6Cycloalkyl, 1,1-dimethyl
Tyl-2-propynyl or 1-cyano-1-methylethyl
And R¹Is hydrogen atom, formyl, methyl carbonyl
Or ethylcarbonyl, and R^TwoIs 1-f
Fluoroethyl or 1-fluoro-1-methylethyl
And the compounds shown.

In a more preferred group of compounds, in the above formula (I), A is CHR ³ R ⁴ (where R ³ and R ⁴
Are the same or different and are each methyl, ethyl, n
-Propyl, i-propyl, n-butyl, sec-butyl, i-butyl, tert-butyl, cyclopentyl,
Cyclohexyl, 2-fluoroethyl, 2-chloroethyl, 1-fluoroethyl, 3-fluoropropyl or 3
-Chloropropyl, provided that the total number of carbon atoms of R ³ and R ⁴ is 4 or more), cyclohexyl substituted with trifluoromethyl, 1,1-dimethyl-2-propynyl or 1-cyano-1-methyl Compounds which represent ethyl, R ¹ represents a hydrogen atom, formyl, methylcarbonyl or ethylcarbonyl, and R ² represents 1-fluoroethyl or 1-fluoro-1-methylethyl.

Specific examples of the compound of the formula (I) of the present invention are shown in Table 1 below.

[0019]

[Table 1]

[0020]

[Table 2]

[0021]

[Table 3]

[0022]

[Table 4] The production method (a) of the compound of the formula (I) can be represented by the following reaction formula A when, for example, 1-ethylpropylbiguanide hydrochloride and methyl 1-fluoro-1-methylpropionate are used as raw materials.

[0023]

Embedded image The production method (b) of the compound of the formula (I) is, for example, a method in which N- (1-ethylpropyl) -6- (1-fluoro-
1-methylethyl) -1,3,5-triazine-2,4-
When a diamine and acetyl chloride are used, they can be represented by the following reaction formula B.

[0024]

Embedded image In the production method (c) of the compound of the formula (I), for example, N- (1-ethylpropyl) -6- (1-fluoro-
1-methylethyl) -1,3,5-triazine-2,4-
When using a diamine and acetic anhydride, it can be represented by the following reaction formula C.

[0025]

Embedded image The production method (d) of the compound of the formula (I) is carried out, for example, by using N- (1-ethylpropyl) -6- (1-fluoro-
1-methylethyl) -1,3,5-triazine-2,4-
When a diamine and ethyl acetate are used, the following reaction formula D
Is represented by

[0026]

Embedded image In the method (e) for producing the compound of the formula (I), for example, N- (1-ethylpropyl) -6- (1-fluoro-1-methylethyl) -1,3,5-triazine-
When 2,4-diamine and acetic acid are used, they can be represented by the following reaction formula E.

[0027]

Embedded image The above-mentioned production method (a) can be carried out according to the method described in the above-mentioned prior document. At that time, the compound of the formula (II) used as a raw material can be produced, for example, by the following production method (f). Production method (f):

Formula A-NH ₂ .HX ¹ (VIII) wherein A and X ¹ are as defined above,

[0029]

Embedded image A method of reacting with a compound represented by the formula:

Typical examples of the compound of the formula (II) are as follows. 1-methylbutyl biguanide hydrochloride, 1,2-dimethylpropyl biguanide hydrochloride, 1.3
-Dimethylbutylbiguanide hydrochloride, 1-ethylpropylbiguanide hydrochloride, 1-ethylbutylbiguanide hydrochloride, 1-ethyl-2-methylpropylbiguanide hydrochloride, 1-ethylpentylbiguanide hydrochloride, 1-ethyl-2-methyl Butyl biguanide hydrochloride, 1-ethyl-3
-Methylbutyl biguanide hydrochloride, 1-ethyl-2,2
-Dimethylpropylbiguanide hydrochloride, 1-cyclopropylpropylbiguanide hydrochloride, 1-cyclopentylpropylbiguanide hydrochloride, 1-cyclohexylpropylbiguanide hydrochloride, 1-propylbutylbiguanide hydrochloride, 1-isopropylbutylbiguanide hydrochloride, 1- Propylpentylbiguanide hydrochloride, 1-isopropyl-
2-methylpropylbiguanide hydrochloride, 1-isopropylpentylbiguanide hydrochloride, 1-butylpentylbiguanide hydrochloride, 1-isobutylpentylbiguanide hydrochloride, 1,5-dimethyl-hexylbiguanide hydrochloride,
-Pentylhexylbiguanide hydrochloride, 1-ethyl-3
-Fluoropropyl biguanide hydrochloride, 3-chloro-1
-Ethylpropyl biguanide hydrochloride, 1-ethyl-2-
Fluoropropyl biguanide hydrochloride, 1-ethyl-4-
Fluorobutylbiguanide hydrochloride, 4-chloro-1-ethylbutylbiguanide hydrochloride, 2-trifluoromethylcyclohexylbiguanide hydrochloride, 3-trifluoromethylcyclohexylbiguanide hydrochloride, 4-trifluoromethylcyclohexylbiguanide hydrochloride, 1, 1-dimethyl-2-propynyl biguanide hydrochloride, 1-cyano-1-methylethyl biguanide hydrochloride and the like.

The above production method (f) can be carried out according to the method described in the above-mentioned prior art.

The compound of the formula (VIII) used as a raw material in the above-mentioned production method (f) is well-known in the field of organic chemistry, and is described, for example, in Experimental Chemistry, edited by The Chemical Society of Japan, Vol. 1339, 1978, published by Maruzen; J. Am. Chem. Soc., 75 , 3212 (195)
3); J. Am. Chem. Soc., 78 , 860 (195)
6); J. Am. Chem. Soc., 66 , 1517 (194)
4); Angew. Chem. Int. Ed., 7 , 919 (196)
8); J. Chem. Soc., 2348 (1926); Synthes
is, 717 (1980); Org. React., 3 , 267
(1946); J. Chem. Soc., 267 (1941); O
rg. React., 3 , 307 (1946); Org. React.,
3 , 337 (1946); J. Org. Chem. USSR, 16 ,
1031 (1980); Farmaco Ed. Sci, 22 , 10,
37 (1967); J. Biol. Chem., 120 , 772.
(1937); WO 92/12121; EP-A1
76327; CS-B233428; DE-A 284
It can be synthesized by the method described in 3480 or the like or a method equivalent thereto.

Specific examples of the compound of the formula (VIII) are as follows. 1-methylbutylamine hydrochloride,
1,2-dimethylpropylamine hydrochloride, 1,3-dimethylbutylamine hydrochloride, 1-ethylpropylamine hydrochloride, 1-ethylbutylamine hydrochloride, 1-ethyl-2-
Methylpropylamine hydrochloride, 1-ethylpentylamine hydrochloride, 1-ethyl-2-methylbutylamine hydrochloride, 1-ethyl-3-methylbutylamine hydrochloride, 1-
Ethyl-1,1-dimethylpropylamine hydrochloride, 1-
Cyclopropylpropylamine hydrochloride, 1-cyclopentylpropylamine hydrochloride, 1-cyclohexylpropylamine hydrochloride, 1-propylbutylamine hydrochloride,
-Isopropylbutylamine hydrochloride, 1-propylpentylamine hydrochloride, 1-isopropyl-2-methylpropylamine hydrochloride, 1-propylpentylamine hydrochloride, 1-isopropyl-2-methylpropylamine hydrochloride, 1-isopropylpentyl Amine hydrochloride, 1-butylpentylamine hydrochloride, 1-isobutylpentylamine hydrochloride, 1,5-dimethylhexylamine hydrochloride,
-Pentylhexylamine hydrochloride, 1-ethyl-3-fluoropropylamine hydrochloride, 3-chloro-1-ethylpropylamine hydrochloride, 1-ethyl-2-fluoropropylamine hydrochloride, 1-ethyl-4-fluoro Butylamine hydrochloride, 4-chloro-1-ethylbutylamine hydrochloride, 2-trifluoromethylcyclohexylamine hydrochloride, 3-trifluoromethylcyclohexylamine hydrochloride, 4-trifluoromethylcyclohexylamine hydrochloride, 1,1-dimethyl -2-propynylamine hydrochloride,
1-cyano-1-methylethylamine hydrochloride and the like.

The compound of the formula (IX) used as a starting material in the above-mentioned production method (f) is known per se,
It can be manufactured by a method well known in the field of organic chemistry.

The compound of the formula (III) used as a raw material in the above-mentioned production method (a) is known per se,
For example, DE-A 4131242, EP-A 850
911, EP-A 468681, JP-A-5-3018
No. 44, J. Org. Chem., 33 , 4279 (196)
It can be produced according to the method described in 8). Specific examples thereof include methyl 1-fluoropropionate,
-Ethyl fluoropropionate, propyl 1-fluoropropionate, butyl 1-fluoropropionate, 1-
Methyl fluoro-1-methylpropionate, ethyl 1-fluoro-1-methylpropionate, 1-fluoro-1
Propyl-methylpropionate, butyl 1-fluoro-1-methylpropionate, and the like.

The compound of the formula (Ia) used as a starting material in the above-mentioned processes (b), (c), (d) and (e) is a novel compound encompassed by the formula (I),
For example, it can be obtained by reacting the compound of the formula (II) with the compound of the formula (III) under the same conditions as in the production method (a) described below. Specific examples are as follows. N- (1-methylbutyl) -6- (1-
(Fluoro-1-methylethyl) -1,3,5-triazine-2,4-diamine, N- (1,2-dimethylpropyl)
-6- (1-Fluoroethyl) -1,3,5-triazine-2,4-diamine, N- (1,3-dimethylbutyl)-
6- (1-fluoro-1-methylethyl) -1,3,5-
Triazine-2,4-diamine, N- (1,5-dimethylhexyl) -6- (1-fluoro-1-methylethyl)
-1,3,5-triazine-2,4-diamine, N- (1
-Ethylpropyl) -6- (1-fluoroethyl)-
1,3,5-triazine-2,4-diamine, N- (1-
Ethylpropyl) -6- (1-fluoro-1-methylethyl) -1,3,5-triazine-2,4-diamine, N
-(1-ethylbutyl) -6- (1-fluoroethyl)
-1,3,5-triazine-2,4-diamine, N- (1
-Ethylbutyl) -6- (1-fluoro-1-methylethyl) -1,3,5-triazine-2,4-diamine, N
-(1-ethyl-2-methylpropyl) -6- (1-fluoro-1-methylethyl) -1,3,5-triazine-
2,4-diamine, N- (1-ethylpentyl) -6
(1-Fluoro-1-methylethyl) -1,3,5-triazine-2,4-diamine, N- (1-ethyl-2-methylbutyl) -6- (1-fluoro-1-methylethyl)- 1,3,5-triazine-2,4-diamine, N-
(1-ethyl-3-methylbutyl) -6- (1-fluoro-1-methylethyl) -1,3,5-triazine-2,
4-diamine, N- (1-ethyl-2,2-dimethylpropyl) -6- (1-fluoro-1-methylethyl)-
1,3,5-triazine-2,4-diamine, N- (1-
Cyclopropylpropyl) -6- (1-fluoro-1-
Methylethyl) -1,3,5-triazine-2,4-diamine, N- (1-cyclopentylpropyl) -6- (1
-Fluoro-1-methylethyl) -1,3,5-triazine-2,4-diamine, N- (1-cyclohexylpropyl) -6- (1-fluoro-1-methylethyl)-
1,3,5-triazine-2,4-diamine and the like.

The formula (IV) used as a raw material in the above production methods (b), (c), (d) and (e),
The compounds (V), (VI) and (VII) are well-known compounds in the field of organic chemistry.

Specific examples of the compound of the formula (IV) include acetyl chloride, acetyl bromide, propionyl chloride and the like. Specific examples of the compound of the formula (V) include acetic anhydride,
Specific examples of the compound of the formula (VI) include methyl formate, ethyl formate, n-propyl formate, n-butyl formate, methyl acetate, ethyl acetate, n-propyl acetate, and n-acetic acid. Butyl, methyl propionate, ethyl propionate, n-propyl propionate,
N-butyl propionate and the like;
Specific examples of the compound of I) include formic acid, acetic acid, propionic acid and the like.

The reaction of the production method (a) can be carried out in a suitable diluent. Examples of the diluent used in this case include alcohols such as methanol, ethanol, isopropanol, butanol, and the like. Ethylene glycol; ethers such as ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF),
Diethylene glycol dimethyl ether (DGM); ketones such as acetone, methyl ethyl ketone (ME
K), methyl isopropyl ketone, methyl isobutyl ketone (MIBK) and the like.

The production method (a) can be carried out in the presence of a base. Examples of the base that can be used at that time include inorganic salts (for example, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, water). Lithium oxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, etc.),
Inorganic alkali metal amides (eg, lithium amide,
Sodium amide, potassium amide, etc.), alkyl alcoholates (eg, sodium methoxide, sodium ethoxide, potassium tert-butoxide), tertiary amines, dialkylanilines, and pyridines (eg, triethylamine, 1,1,4) 1,4-tetraethylenediamine (TMEDA), N, N-dimethylaniline, N, N-diethylaniline, pyridine, 4-dimethylaminopyridine (DMAP), 1,4-diazabicyclo [2.2.2] octane (DABCO) 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU)
Etc.), organic lithium compounds (eg, methyl lithium,
n-butyllithium, sec-butyllithium, tert-
Butyl lithium, phenyl lithium, lithium diisopropylamide, n-butyl lithium DABCO, n-
Butyllithium DBU, n-butyllithium TME
DA etc.).

The reaction of process (a) can be carried out within a substantially wide temperature range. Generally about 0 to about 1
The reaction can be carried out at a temperature of 50 ° C., preferably at a temperature of about 25 to about 100 ° C. under normal pressure, but may be carried out under elevated or reduced pressure in some cases.

In carrying out the production method (a), for example, 1 to 2 mol of the compound of the formula (III) is added to 1 mol of the compound of the formula (II) in a diluent ethanol to give a base such as sodium ethoxide 1 By reacting in the presence of ２2 mol, the desired compound of formula (I) can be obtained.

The reactions of the above processes (b), (c), (d) and (e) can be carried out in appropriate dilutions,
Examples of diluents used in this case include water, aliphatic, cycloaliphatic and aromatic hydrocarbons (optionally chlorinated), for example, benzene, toluene, xylene, dichloromethane, chloroform, Carbon tetrachloride, 1,
2-dichloroethane, chlorobenzene; ethers such as ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (TH
F); ketones, for example, acetone, methyl ethyl ketone (MEK), methyl isopropyl ketone, methyl isobutyl ketone (MIBK); nitriles, for example, acetonitrile, propionitrile; alcohols, for example, methanol, ethanol, isopropanol, butanol, Ethylene glycol; esters such as ethyl acetate, amyl acetate; acid amides such as dimethylformamide (DMF), dimethylacetamide (DM
A), N-methylpyrrolidone, 1,3-dimethyl-2-
Imidazolidinone, hexamethylphosphoric amide (HMPA); bases such as pyridine;

The production processes (b), (c) and (d) can be carried out in the presence of a base. Examples of the base which can be used in this case include inorganic salts (for example, sodium hydrogen carbonate, potassium hydrogen carbonate) , Sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, etc.), alkyl alcoholates (eg, sodium methoxide, sodium ethoxide, potassium tert-butoxide, etc.), tertiary amines , Dialkylaminoanilines and pyridines (for example, triethylamine, 1,1,4,4-tetramethylethylenediamine (TMEDA), N, N-dimethylaniline, N, N-diethylaniline, pyridine, 4-dimethylaminopyridine ( DMAP) 1,4-diazabicyclo [2.2.2]
Octane (DABCO), 1,8-diazabicyclo [5.
4.0] undec-7-ene (DBU) and the like.

The production method (e) can be carried out in the presence of a condensing agent. Examples of the condensing agent that can be used at that time include dicyclohexylcarbodiimide, acetic anhydride, thionyl chloride,
Examples thereof include phosphorus pentachloride, phosphorus oxychloride, aluminum oxide, silicon tetrachloride, and titanium tetrachloride.

The reactions of processes (b), (c), (d) and (e) can be carried out within a substantially wide temperature range, but generally from about -20 to about 150 ° C, preferably from about -20 ° C to about 150 ° C. The reaction can be carried out at a temperature of 0 to about 100 ° C. under normal pressure, but may be carried out under pressurized or reduced pressure in some cases.

In the reaction of the production method (b), the compound of the formula (IV) is usually used in the presence of 0.8 to 2.0 mol of the compound of the formula (IV) per 1 mol of the compound of the formula (Ia) in the presence of a base such as 1 to 3 mol of triethylamine. The reaction can be performed under the following conditions.

The reaction of the production method (c) is usually carried out by adding 0.8 to 2.0 mol of the compound of the formula (V) to 1 mol of the compound of the formula (Ia) in the presence of a base such as 1 to 3 mol of triethylamine. The reaction can be performed under the following conditions.

In the reaction of the production method (d), usually, 0.8 to 2.0 mol of the compound of the formula (VI) is added to 1 mol of the compound of the formula (Ia), and 1 to 3 mol of a base such as sodium methoxide. By reacting in the presence of

In the reaction of the production method (e), the compound of the formula (VII) is usually used in an amount of from 0.8 mol to 1 mol of the compound of the formula (Ia).
2.0 moles can be reacted by reacting in the presence of a condensing agent such as dicyclohexylcarbodiimide.

The active compound of the formula (I) of the present invention has excellent herbicidal activity as shown in the test examples described below.
It can be used as a herbicide for controlling weeds. Here, "weeds" broadly means all plants that grow in undesirable places.

The compounds of the present invention act as non-selective or selective herbicides depending on the concentration used. The active compounds according to the invention can be used, for example, as selective herbicides between the following weeds and cultivated plants.

Dicotyledonous weeds: mustard (Sinapis), mamegunbainazuna (Leipidium), Jaegura kinutasou (Galium), Shikoku (Stellaria), Akaza aritasou (Chenopodium), nettle (Urtica), Hangangsou noborogiku kion (Senecio) ), Amaranthus, Portulium
aca), Onami fir (Xanthium), morning glory (Ipomoea),
Willow (Polygonum), Ragweed (Ambrosia), Nozami / Fujizami (Cirsium), Nogeshi (Sonchus),
Eggplant potato (Solanum), wild pepper (Roripp)
a), Odorikosou (Lamium), stag beetle, Inunofuguri (Veronica), narcissus morning glory (Datura),
Violet panicles (Viola), Chishimadoro (Galeopsi)
s), poppies (Papaver), cornflowers (Centaurea),
Ginkgo biloba (Galinsoga), stag beetle (Rotala),
Cultivars of dicotyledon such as Azena (Lindernia): Cotton (Gossy)
pium), soybean (Glycine), chard beet sugar beet (Beta), carrot (Daucus), kidney bean Aiomada (Phaseolus), pea (Pisum), eggplant potato (Solanum), flax (Linum), sweet potato asagao (Ipomoea) ), Broad bean Nantenhagi (Vici)
a), tobacco (Nicotiana), tomato (Lycopersicon),
Peanut (Arachis), Brassica napus cabbage cabbage (Brassica), Akinonogeshi (Lactuc)
a), Kiuri melon (Cucumis) pumpkin (Cucurbit)
a) etc.

Monocotyledon weeds: Millet (Echinochloa), Enochoro millet (Setaria), millet (Panicum), Meishishiba (Digitaria), Awagaeri timothy (Phleum), Strawberry squirrel, Poa, and Festuca (Festuca) , Ohishiba Shikokubie (Ele
usine), Dokumugi (Lolium), Kitsuneya Inugi (Bromus), Oats oats (oat) (Av
ena), Cyperus papyrus, Sycamore, Cyperus, Sorghum, Sorghum (Ag)
ropyron), Eel (Monochoria), Tentsuki (Fimbris)
tylis), Omodaka Kwai (Sagittaria), Harii
Kuroguwai (Eleocharis), firefly, ukiyagura futoyi (Scirpus), sparrow fin (Paspalum), platypus (Ischaemum), nukabo (Agrostis), Alpinecurus (Alopecurus) and Cynodon.

Monocotyledon cultivation plants: rice (Oryza), corn hop corn (Zea), wheat (Triticum), barley (Hordeum), oats oats (oats) (Avena), rye (Secale), sorghum (Sorghu)
m), millet (Panicum), sugarcane vaseobana (Sacc
harum), pineapple (Ananas), asparagus (Asp)
aragus), leek and leek (Allium).

Use of the active compounds of the formula (I) according to the invention
The present invention is not limited to the above plants, and can be similarly applied to other plants. Further, depending on the concentration used, the active compound of the present invention can non-selectively control weeds.For example, it can be used in industrial sites such as industry, railway tracks, roads, plantations, and non-plantations. it can.

Furthermore, the active compounds according to the invention can be used for weed control in perennial plant cultivation, for example plantations, ornamental plantations, orchards, vineyards, citrus orchards, nut orchards, Banana plantation, coffee plantation, tea plantation, rubber plantation, guinea oil palm plantation,
The present invention can be applied to cocoa cultivation sites, small orchards, hop cultivation sites, and the like, and can also be applied to selective weed control in annual plant cultivation.

The active compounds of the formula (I) according to the invention can be brought into the customary pharmaceutical forms for use. Such formulations include, for example, solutions, emulsions, wettable powders,
Suspensions, powders, soluble powders, granules, tablets, suspension emulsion concentrates, microcapsules in polymeric substances, jumbo preparations and the like can be mentioned.

These preparations can be prepared in a manner known per se, for example, by adding the active compound to extenders, ie, liquid and / or solid diluents, if necessary with surfactants. That is, emulsifier and / or dispersant and / or
Alternatively, it can be produced by mixing with a foam forming agent or the like.

When water is used as the spreading agent, an organic solvent can be used as an auxiliary solvent. Examples of the liquid diluent include aromatic hydrocarbons (eg, xylene, toluene, alkylnaphthalene, etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (eg, chlorobenzenes, ethylene chlorides, methylene chloride, etc.) ), Aliphatic hydrocarbons [eg, cyclohexane and the like or paraffins (eg, mineral oil fractions, mineral and vegetable oils etc.)], alcohols (eg, butanol, glycol and ethers and esters thereof), ketones (eg, acetone,
Examples thereof include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc., strong polar solvents (eg, dimethylformamide, dimethyl sulfoxide, etc.), water and the like.

Examples of solid diluents include ammonium salts, soil natural minerals (eg, kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite, diatomaceous earth, etc.) and soil synthetic minerals (eg, highly dispersed silicic acid, alumina, silica Acid salts). Solid carriers for granules include, for example, crushed and fractionated rocks (eg, calcite, marble, pumice, sepiolite, dolomite, etc.), synthetic particles of inorganic and organic powders, fine particles of organic substances ( For example, sawdust, coconut, corn cob, tobacco stem, etc.).

Examples of the emulsifier and / or foaming agent include nonionic and anionic emulsifiers [eg, polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers (eg, alkylaryl polyglycol ethers, alkyl sulfonates, Alkyl sulfates, aryl sulfonates, etc.]] and albumin hydrolysis products.

Suitable dispersants include, for example, lignin sulfite waste liquor and methylcellulose.

Fixing agents can also be used, if desired, in the preparations (powder, granules, jumbo, emulsion), such as carboxymethylcellulose, natural and synthetic polymers (eg Arabic) Rubber, polyvinyl alcohol, polyvinyl acetates, etc.), natural phospholipids (eg, cephalins and lecithins),
Examples include synthetic phospholipids. Further, mineral and vegetable oils can be used as additives.

A coloring agent may be added. Examples of the coloring agent include inorganic pigments such as iron oxide, titanium oxide and Prussian blue; organic dyes such as alizarin dye, azo dye and metal phthalocyanine dye; Iron, manganese,
Trace elements such as salts of metals such as boron, copper, cobalt, molybdenum, zinc and the like can be mentioned.

The preparations generally contain the active ingredient in an amount of 0.5.
It can be contained in the range of 1 to 95% by weight, preferably 0.5 to 90% by weight.

The active compounds of the present invention can be used as they are or in the form of their preparations for controlling weeds, and can also be used as admixtures with known herbicides. May be prepared in advance in the final preparation form, or may be a tank mix for use.

The active compounds of the formula (I) of the present invention
Mixtures with safeners are also possible, which allows for a wider application as a selective herbicide.

Examples of the safener include 1- (α, α-dimethylbenzyl) -3-p-tolylurea.

The active compounds of the formula (I) according to the invention can be used as such or in the form of the abovementioned preparations in customary manner, for example by
Watering, spraying, atomizin
g), powdering or granulation can be applied.

The active compounds of the formula (I) according to the invention can be applied both before and after germination of the plants. They can also be incorporated into the soil before sowing.

The application rate of the active compound is not strictly limited, and the desired effect, the type of the target plant,
It can be varied over a wide range depending on the place of application, the time of application, etc., but as a rough guide, about 0.001 kg to about 10 k as active compound per hectare
g, preferably in the range of about 0.01 kg to about 5 kg.

Next, the production and use of the compound of the present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. In addition,
“Parts” are “parts by weight” unless otherwise specified.

[0074]

EXAMPLES Synthesis Example 1

[0075]

Embedded image 1-ethylpropylamine hydrochloride (4.94 g) was added to 1,2
Suspended in dichlorobenzene (50 ml), to which cyanoguanidine (3.36 g) was added;
The mixture was heated and stirred at 0 ° C. for 3 hours. After completion of the reaction, the resulting precipitate was cooled and collected by filtration, and washed three times with ether (10 ml). Then, the solvent was removed under reduced pressure to obtain 1-ethylpropylbiguanide hydrochloride. This was used for the next reaction without further purification.

Next, sodium metal (1.10 g) was added to methanol (150 ml), and after the metal sodium was completely dissolved, 1-ethylpropylbiguanide hydrochloride was added. Then, 1-fluoro-1-methylpropione was added. Methyl acid (5.29 g) was added, and the mixture was stirred at room temperature for 48 hours. After completion of the reaction, methanol was distilled off under reduced pressure, water (80 ml) was added to the residue, and ethyl acetate (120 ml) was added.
Extracted using. After drying the ethyl acetate layer with anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The crude product was purified by silica gel column chromatography (solvent ether: n-hexane = 1: 1), and the desired N- (1-ethylpropyl) -6- (1-fluoro-1-methylethyl)-
1,3,5-triazine-2,4-diamine (3.20 g)
I got

Melting point: 104-106 ° C. Synthesis Example 2

[0078]

Embedded image N- (1-ethylpropyl) -6- (1-fluoro-1
-Methylethyl) -1,3,5-triazine-2,4-diamine (1 g) and triethylamine (5.63 g) were suspended in THF (30 ml), and acetyl chloride (3.39 g) was added at 5 ° C. The suspension was added dropwise and refluxed for 2 hours. A saturated sodium bicarbonate solution (6
0 ml), extracted with ethyl acetate (80 ml) and dried over anhydrous magnesium sulfate. After evaporating the solvent, the crude product was purified by silica gel column chromatography (solvent ether: n-hexane = 1: 1), and N-acetyl-N ′-(1-ethylpropyl) -6- (1-fluoro) was purified. -2-methylethyl) -1,3,5-triazine-2,4
-Diamine (1.17 g) was obtained.

Melting point 109-111 ° C. The compounds obtained in the same manner as in Synthesis Examples 1 and 2 are shown in Table 2 below together with the compounds synthesized in Synthesis Examples 1 and 2.

[0080]

[Table 5] Test Example 1 : Pre-emergence soil treatment test for upland weeds Preparation method: Carrier: acetone 5 parts by weight Emulsifier: benzyloxy polyglycol ether 1 part by weight 1 part by weight of the active compound was mixed with the above amounts of the carrier and emulsifier, An emulsion is obtained. A predetermined amount of the emulsion is diluted with water to prepare a reagent. Test method: 120cm filled with field soil in greenhouse
Each of the ^two pots was sowed and covered with seeds of barnyardgrass, enokorogusa, Inubiju and Inudate, and the prescribed amount of the above-mentioned chemicals was evenly applied to the soil surface of each test pot. Four weeks after spraying, the degree of herbicidal effect was examined. In addition, the herbicidal effect was evaluated as 100% when completely killed, and 0% when equivalent to the untreated section. Result: Compound Nos. 5, 6, 7 and 8 killed 90% or more of the target weeds (barnyardgrass, enokologa, branilium and inudate) at an application rate of 1 kg / ha as an active ingredient. Test Example 2 : Test of post-emergence foliage treatment on field weeds Test method: 120 cm of field soil packed in a greenhouse
^Two pots were sown with seeds of barnyardgrass, enokorogusa, branilium, and inudate and covered with soil. Ten days after sowing and covering the soil (weeds have an average of two leaves), a predetermined amount of the drug prepared in the same manner as in Test Example 1 was evenly applied to the foliage of the test plant in each test pot. Three weeks after spraying, the degree of herbicidal effect was examined. Result: Compound Nos. 1, 2, 4 and 8 killed 100% of target broadleaf weeds (Inuville and Inudate) at an application rate of 1 kg / ha as an active ingredient. Formulation Example 1 (Granules) To a mixture of 10 parts of compound No. 1, 30 parts of bentonite (montmorillonite), 58 parts of talc (talc) and 2 parts of lignin sulfonate, 25 parts of water is added, kneaded well, and extruded. Granules of 10 to 40 mesh are formed by a granulator and dried at 40 to 50 ° C. to obtain granules. Formulation Example 2 (Emulsion) 30 parts of Compound No. 5, 55 parts of xylene, 8 parts of polyoxyethylene alkylphenyl ether and 7 parts of calcium alkylbenzenesulfonate are mixed and stirred to form an emulsion. Formulation Example 3 (Wettable powder) 15 parts of compound No. 6, a mixture of white carbon (hydrated amorphous silicon oxide fine powder) and powdered clay (1:
5) 80 parts, sodium alkylbenzene sulfonate 2
Parts and 3 parts of sodium alkylnaphthalenesulfonate formalin condensate are pulverized and mixed to obtain a wettable powder. Formulation Example 4 (hydrated granules) Compound No. 8 (20 parts), ligninsulfonic acid sodium salt (30 parts), bentonite (15 parts) and calcined diatomaceous earth powder (35 parts) were sufficiently mixed, water was added, and the mixture was extruded with a 0.3 mm screen. Dry to form hydrated granules.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H011 AB01 DA02 DA15 DA16 DC05 DC07 DC08 DD03 DD04

Claims (4)

[Claims] 1. The formula: embedded image In the formula, A is CHR ³ R ⁴ (where R ³ and R ⁴ are the same or different and each represents C _1-6 alkyl, C _3-7 cycloalkyl or C _1-4 haloalkyl, provided that R ³ And R ⁴
The total number of carbon atoms is 4 or more is), C ₁ haloalkyl substituted C _3-6 cycloalkyl, C _3-6 alkynyl or C
_{Represents 1-4} cyanoalkyl, R ¹ represents a hydrogen atom, formyl or C _1-3 alkylcarbonyl, and R ² represents 1-
1,3,5-triazines represented by the formula showing fluoroethyl or 1-fluoro-1-methylethyl. 2. A is CHR ³ R ⁴ (where R ³ and R ⁴ are the same or different and each is C _1-5 alkyl, C _3-6
Represents cycloalkyl or C _1-3 haloalkyl, provided that
The total number of carbon atoms in R ³ and R ⁴ is 4 or more), C ₁ haloalkyl substituted C _5-6 cycloalkyl, indicates 1,1-dimethyl-2-propynyl or 1-cyano-1-methylethyl, R ¹ is a hydrogen atom, formyl, a methyl carbonyl or ethylcarbonyl, and, R ² is 1-fluoroethyl or 1-fluoro-1 compound according to claim 1 showing a methylethyl. 3. A is CHR ³ R ⁴ (where R ³ and R ⁴ are the same or different and are each methyl, ethyl, n-
Propyl, i-propyl, n-butyl, sec-butyl, i-butyl, tert-butyl, cyclopentyl,
Cyclohexyl, 2-fluoroethyl, 2-chloroethyl, 1-fluoroethyl, 3-fluoropropyl or 3
-Chloropropyl, provided that the total number of carbon atoms of R ³ and R ⁴ is 4 or more), cyclohexyl substituted with trifluoromethyl, 1,1-dimethyl-2-propynyl or 1-cyano-1-methyl It indicates ethyl, R ¹ is a hydrogen atom, formyl, a methyl carbonyl or ethylcarbonyl, and, R ² is 1-fluoroethyl or 1-fluoro-1 compound according to claim 1 showing a methylethyl. 4. A herbicide comprising the compound according to claim 1 as an active ingredient.