JPH0892225A - Triazoleglycolic acid amide derivative - Google Patents

Abstract

PURPOSE: To obtain a triazoleglycolic acid amide derivative safe to crop and having high herbicidal effect on field and paddy weeds. CONSTITUTION: This compound is expressed by formula 1 [R<1> is H, CN, NO2 , carbamoyl or a halogen; R<2> is a 1-6C alkyl, (substituted) phenyl or (substituted) pyridyl; R<3> and R<4> are each H, a 1-6C alkyl, 3-6C cycloalkyl, 2-4C alkenyl, 2-4C alkynyl, phenyl-substituted 1-4C alkyl, (substituted) phenyl, (substituted) pyridyl, etc., or forms, together with the N-atom bound thereto, a 3- to 9-membered ring which may contain O, S, N, CO, SO2 and/or unsaturated bond, may be substituted with a 1-4C alkyl, OH, halogen, phenyl, etc., may be cross-linked by an alkylene, or may be condensed with a benzene ring], e.g. 2-(3-chloro-1- phenyl-1,2,4-triazol-5-yloxy) acetic acid piperidide. This compound of formula I is obtained by reaction of a compound of formula 2 with a compound of formula 3 in the presence of a base.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to novel triazole glycolamide derivatives and herbicides containing them as an active ingredient.

[0002]

2. Description of the Related Art At present, many herbicides have been put into practical use as herbicides for paddy fields and widely used as single agents and mixed agents. There are many types of paddy weeds, and many herbicides effective for annual broadleaf weeds are known, and the number of herbicides effective for perennial weeds has been increasing in the last few years.

[0003] However, as one of the important weeds in paddy fields, and the most frequent growing area, Nobie belongs to the same grass family as paddy rice, it does not cause any phytotoxicity to paddy rice and is
In particular, little herbicide has a high effect on highly grown individuals. As a prior art having a structure similar to that of the present invention, a part of triazole glycolic acid amides is disclosed in DE4038811A1, but as in the present invention, a hydrogen atom at the 3-position on the 1,2,4-triazole ring,
A compound having a cyano group, a nitro group, a carbamoyl group or a halogen atom and having a glycolic acid amide bonded at the 5-position has never been known and is a novel compound.

[0004]

[Means for Solving the Problems] The present inventors have continued to study for many years in order to develop a herbicide having selectivity for important crops, and have compounds having higher herbicidal activity and wider selectivity. The herbicidal properties of many compounds have been investigated in order to produce As a result, formula (1):

[0005]

[Chemical 2]

[Wherein R¹Is hydrogen atom, cyano group, nit
R group, carbamoyl group or halogen atom, R²
Is C_1-6Alkyl group, phenyl group (C_1-4An alkyl group,
C_1-4Haloalkyl group, C_1-4Alkoxy group, cyano
A group selected from a group, a nitro group and a halogen atom, or
It may be substituted with two or more substituents. ),
Lysyl group (C _1-4Alkyl group, C_1-4A haloalkyl group,
C_1-4Alkoxy, cyano, nitro and halogen
Position by one or more substituents selected from
It may be replaced. ), R³And R^FourIs it
Independently hydrogen atom, C_1-6Alkyl group, C_3-6Shiku
Lower alkyl group, C_2-4Alkenyl group, C_2-4Alkynyl
Group, C_3-6C substituted with a cycloalkyl group_1-2Archi
Group, C_1-4Alkoxy C_1-4Alkyl group, phenyl group
(C_1-4Alkyl group, C_1-4Haloalkyl group, C_1-4A
Lucoxy group, cyano group, nitro group and halogen atom
Substituted by one or more substituents selected from
May be. ) Replaced by C_1-4An alkyl group,
Phenyl group (C_1-4Alkyl group, C_1-4Haloalkyl
Group, C_1-4Alkoxy, cyano, nitro and ha
Depending on one or more substituents selected from the rogen atom
May be replaced. ), A pyridyl group (C_1-4Al
Kill group, C_1-4Haloalkyl group, C_1-4An alkoxy group,
1 selected from cyano group, nitro group and halogen atom
Or may be substituted by two or more substituents
Yes. ) Replaced by C _1-4Alkyl group, pyridyl
Group (C_1-4Alkyl group, C_1-4Haloalkyl group, C_{1- Four}
Alkoxy, cyano, nitro and halogen atoms
Substituted by one or more substituents selected from
May be. ), C_1-4Alkoxy group (provided that R^FourWhen
R^FiveDoes not simultaneously represent an alkoxy group. ) Or
Cyano C_1-4Represents an alkyl group.

However, R ⁴ and R ⁵ may form a 3- to 9-membered ring together with the nitrogen atom to which R ⁴ and R ⁵ are bonded, and an oxygen atom, a sulfur atom, a nitrogen atom, a carbonyl group, a sulfonyl group or an unsaturated group is present in the ring. The ring may contain one or more bonds, and the ring has a C _1-4 alkyl group, a C _1-4 alkoxy group, a hydroxyl group, a halogen atom, a C _1-4 haloalkyl group, a C _1-4 alkoxycarbonyl group, phenyl. It may be substituted by a group or a benzyl group, the ring may be bridged by C _1-4 alkylene and the ring may be fused by a benzene ring. ] The triazole glycolamide derivative represented by the following (hereinafter, the compound of the present invention) is found to have a high herbicidal effect against Novier and other paddy field weeds and a high degree of safety against paddy rice, and further, the amount of the drug used is small. Completed the invention.

The substituents R ¹ , R ² , R ³ and R ⁴ of the compound of the present invention are listed specifically below. However, the symbols have the following meanings. Me: methyl group, Et: ethyl group, Pr-n: normal propyl group, Pr-iso: isopropyl group, Bu-
n: normal butyl group, Bu-iso: isobutyl group,
Bu-sec: Secondary-butyl group, Bu-ter
t: tertiary butyl group, Pen-n: normal pentyl group, Hex-n: normal hexyl group, Pr-cy
c: cyclopropyl group, Bu-cyc: cyclobutyl group, Pen-cyc: cyclopentyl group, Hex-cy
c: cyclohexyl group, Ph: phenyl group, Py: pyridyl group

[Specific Examples of Substituent R ¹ of the Compound of the Present Invention] H,
CN, F, Cl, Br, I, NO ₂ , CONH ₂

[Specific Examples of Substituent R ² of the Compound of the Present Invention] H,
Me, Et, Pr-n, Pr-iso, Bu-n, Bu-iso, Bu-sec, Bu-t
ert, Pen-n, Hex-n, Ph, 2-Cl-Ph, 3-Cl-Ph, 4-Cl-Ph,
2,4-Cl ₂ -Ph, 2-F-Ph, 3-F-Ph, 4-F-Ph, 2-F-4-Cl-Ph, 2
-Br-Ph, 3-Br-Ph, 4-Br-Ph, 2-Me-Ph, 3-Me-Ph, 4-Me-P
h, 2,4-Me ₂ -Ph, 2,6-Me ₂ -Ph, 2-MeO-Ph, 3-MeO-Ph, 4-Me
O-Ph, 2-CF ₃ -Ph, 3-CF ₃ -Ph, 4-CF ₃ -Ph, 3,5-Cl ₂ -Ph, 2,6
-Cl ₂ -Ph, 2,3-Cl ₂ -Ph, 2,4,6-Cl ₃ -Ph, 2,3,5-Cl ₃ -Ph,
2,3,4-Cl ₃ -Ph, 2-Cl-4-CF ₃ -Ph, 2,6-Cl ₂ -4-CF ₃ -Ph, 2-N
O ₂ -Ph, 2-CN-Ph, 3-CN-Ph, 4-CN-Ph, 2,5-Cl ₂ -Ph, 3,4-
Cl ₂ -Ph, 2,4- (NO ₂ ) ₂ -Ph, 3-NO ₂ -Ph, 4-NO ₂ -Ph, 2-Py, 3
-Py, 4-Py, 3-Cl-2-Py, 4-Cl-2-Py, 5-Cl-2-Py, 6-Cl-2
-Py, 3-F-2-Py, 4-F-2-Py, 5-F-2-Py, 6-F-2-Py, 3-Br-
2-Py, 4-Br-2-Py, 5-Br-2-Py, 6-Br-2-Py, 3-CF ₃ -2-Py,
4-CF ₃ -2-Py, 5-CF ₃ -2-Py, 6-CF ₃ -2-Py, 3-Cl-5-CF ₃ -2-
Py, 3-Me-2-Py, 4-Me-2-Py, 5-Me-2-Py, 6-Me-2-Py, 3-
NO ₂ -2-Py, 4-NO ₂ -2-Py, 5-NO ₂ -2-Py, 6-NO ₂ -2-Py, 3-P
y, 4-Py

[Specific Examples of Substituents R ³ and R ⁴ of the Compound of the Present Invention] H, Me, Et, Pr-n, Pr-iso, Bu-n, Bu-iso, Bu
-sec, Bu-tert, CHMeCHMe ₂ , Pen-n, Hex-n, Hex-iso, P
r-cyc, Bu-cyc Pen-cyc, Hex-cyc, CH ₂ Pr-cyc, CH ₂ Bu
-cyc, CH ₂ Pen-cyc, CH ₂ Hex-cyc, CH ₂ CH ₂ Pr-cyc, CH ₂ CH =
_{CH 2, CH 2 CH = CHMe} , CH 2 CH 2 CH = CH 2, CH 2 C ≡CH, CH 2 C≡CM
e, CH ₂ OMe, CH ₂ OEt, CH ₂ OPr-n, CH ₂ OBu-n, CH ₂ OBu-iso,
CH ₂ OBu-sec, CH ₂ OBu-tert, CH ₂ CH ₂ OMe, CH ₂ CH ₂ OEt, CH
₂ CH ₂ OPr-n, CH ₂ CH ₂ CH ₂ OMe, CH ₂ CH ₂ CH ₂ OEt, CH ₂ CH ₂ CH ₂ CH
₂ OMe, Ph, 2-Cl-Ph, 3-Cl-Ph, 4-Cl-Ph, 2,4-Cl ₂ -Ph,
3,5-Cl ₂ -Ph, 2,6-Cl ₂ -Ph, 2,3-Cl ₂ -Ph, 2,5-Cl ₂ -Ph, 2-
F-Ph, 3-F-Ph, 4-F-Ph, 2-F-4-Cl-Ph, 2-Br-Ph, 3-Br-P
h, 4-Br-Ph, 2-Me-Ph, 3-Me-Ph, 4-Me-Ph, 2,4-Me ₂ -Ph,
3,5-Me ₂ -Ph, 2,6-Me ₂ -Ph, 2,3-Me ₂ -Ph, 2,5-Me ₂ -Ph, 2
-MeO-Ph, 3-MeO-Ph, 4-MeO-Ph, 2-CF ₃ -Ph, 3-CF ₃ -Ph, 4
-CF ₃ -Ph, 2,4,6-Cl ₃ -Ph, 2,3,5-Cl ₃ -Ph, 2,3,4-Cl ₃ -Ph,
2-NO ₂ -Ph, 2-CN-Ph, CH ₂ Ph, OMe, OEt, OPr-n, OPr-is
o, OBu-n, OBu-iso, OBu-tert, CH ₂ CH ₂ CN, CH ₂ Ph, CHMe
Ph, CMe ₂ Ph, CH ₂ -2-Cl-Ph, CH ₂ -3-Cl-Ph, CH ₂ -4-Cl-Ph,
2-Py, 6-MeO-2-Py, 6-Cl-2-Py, 6-F-2-Py, 5-CF ₃ -2-P
y, 3-Cl-5-CF ₃ -2-Py, 3-Py, 4-Py, CH ₂ -5-Cl-2-Py, CH ₂
-6-Cl-3-Py

[Specific Examples in the Case of Constructing a Saturated 3-9 Member Ring with the Nitrogen Atom to which the Substituents R ³ and R ^{4 of the} Compound of the Present Invention are Bonded]

[0013]

[Chemical 3]

[0014]

[Chemical 4]

Further, a preferred substituent R of the compound of the present invention
Specific listings of ¹ and R ² are as follows. R ¹ : CN, F, Cl R ² : Ph, 2-Py The compound of the present invention can be easily produced by selecting one of the following reaction formulas 1 and 2.

[Reaction Formula 1]

[0017]

[Chemical 5]

[In the formula, R ¹ , R ² , R ³ and R ⁴ have the same meanings as described above, and Z represents a halogen atom or a methanesulfonyl group. ] That is, 5-halogeno (or methanesulfonyl)
-1,2,4-triazoles (2) are reacted with glycolic acid amides (3) in the presence of a base to produce the compound (1) of the present invention
Can be synthesized. As the base, an inorganic base such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium hydride, or pyridine, triethylamine, DB
Organic bases such as U can be used. This reaction proceeds even without solvent, but a solvent can be used if necessary. The solvent used is not particularly limited as long as it is inert to the reaction, for example, hexane, cyclohexane, benzene, an aliphatic or aromatic hydrocarbon such as toluene, diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran and the like. Ketones such as ethers, acetone, methyl ethyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile and propionitrile, acid amides such as dimethylformamide and dimethylacetamide, sulfur-containing polar solvents such as dimethyl sulfoxide and sulfolane, pyridine and the like There are organic bases. The reaction temperature can be arbitrarily selected from the range of -50 ° C to 150 ° C, but is preferably in the range of 0 ° C to 60 ° C.

[Reaction Formula 2]

[0020]

[Chemical 6]

[Wherein R ¹ , R ² , R ³ , R ⁴ and Z
Represents the same meaning as described above, and R ⁵ represents a C _1-6 alkyl group or a phenyl group. ] That is, 5-halogeno (or methanesulfonyl)
-1,2,4-triazoles (2) are reacted with glycolic acid esters (4) in the presence of a base to give triazole glycolic acid esters (5). The base, the solvent and the reaction temperature are in accordance with the reaction formula 2. Further hydrolysis of (5),
The compound (1) of the present invention can be synthesized by halogenating the acid chloride (6) and then reacting it with an amine (7).

The synthetic examples of the compound of the present invention will be specifically described below as Examples, but the present invention is not limited thereto. Example 1 Synthesis of 2- (3-chloro-1-phenyl-1,2,4-triazol-5-yloxy) acetic acid piperidide

[0023]

[Chemical 7]

3,5-dichloro-1-phenyl-1,
0.67 g (3.1 mmol) of 2,4-triazole and 0.44 g (3.1 mmol) of glycolic acid piperidide
0.21 g (3.8 mmol) of potassium hydroxide in powder form was added to the dimethylsulfoxide (5 ml) solution of and the mixture was stirred at room temperature for 0.5 hours. Water (50 ml) was added, and the mixture was extracted twice with ether (50 ml). The ether layer was washed successively with water and a saturated aqueous solution of sodium chloride, dried over anhydrous magnesium sulfate and the solvent was distilled off. The obtained residue was purified by silica gel column chromatography (eluent: ethyl acetate) to obtain the desired product 0 0.8 g was obtained. Oily substance.

Example 2 N-methyl-N-phenyl-2- (3-chloro-1-phenyl-1,2,4-triazol-5-yloxy)
Acetamide synthesis

[0026]

Embedded image

3,5-dichloro-1-phenyl-1,
0.6 g (2.8 mmol) of 2,4-triazole and N
-Methyl-N-phenylglycolic acid amide 0.46 g
Using (2.8 mmol) as a starting material, the reaction and post-treatment were carried out in the same manner as in Example 1 to obtain 0.9 g of the desired product. 138-140 ° C. Example 3 (1) Synthesis of Phenylhydrazonobromoacetonitrile

[0028]

[Chemical 9]

13 g (90 mmol) of cyanoformaldehyde phenylhydrazone in chloroform (800 g)
Is dissolved in N-bromosuccinimide 1 at 0 to 15 ° C.
6 g (90 mmol) was added. After stirring for 1 hour at room temperature,
500 ml of n-hexane was added, the precipitated solid was filtered off, and the solvent of the mother liquor was distilled off to obtain 16 g of the desired product. Melting point 1
20-125 ° C.

(2) Synthesis of N-phenylcyanoformamidrazone

[0031]

[Chemical 10]

16.2 g of phenylhydrazonobromoacetonitrile was dissolved in ethanol (50 ml), and the mixture was mixed at 10 ° C.
At 28% aqueous ammonia (9 ml) was added. After stirring at room temperature for 0.5 hour, the solvent was evaporated under reduced pressure, and ethyl acetate (2
(00 ml) and water (50 ml) were added and extraction operation was performed. The organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and the obtained solid was washed with diisopropyl ether and dried to obtain 3.9 g of the desired product. Melting point 147-150 [deg.] C.

(3) 5-mercapto-1-phenyl-
Synthesis of 1,2,4-triazole-3-carboxylic acid amide

[0034]

[Chemical 11]

3.6 g (23 mmol) of N-phenylcyanoformamidrazone and 3.6 g (46 m of pyridine)
mol) in methylene chloride (40 ml), -20
A solution of 2.6 g (23 mmol) of thiophosgene in methylene chloride (20 ml) was added dropwise at 0 ° C. After stirring at room temperature for 1 hour, 50 ml of a 10% sodium hydroxide aqueous solution was added, and the mixture was vigorously stirred. The aqueous layer is separated and acidified with concentrated hydrochloric acid (pH =
In 1), the precipitated solid was collected by filtration, washed with water and dried to obtain 1.2 g of the desired product. Melting point 200-205 [deg.] C.

(4) 5-methylthio-1-phenyl-
Synthesis of 1,2,4-triazole-3-carboxylic acid amide

[0037]

[Chemical 12]

20 ml of tetrahydrofuran (THF)
Then, 0.24 g (6.0 mmol) of 60% sodium hydride washed with n-hexane was suspended, and 5-mercapto-1-phenyl-1,2,4-triazole-3-
Carboxylic amide 1.2 g (6.0 mmol) THF
(10 ml) solution was added dropwise. After stirring for 10 minutes at room temperature,
Methyl iodide (0.85 g, 6.0 mmol) was added, and the mixture was further stirred at room temperature for 3 hours. The reaction mixture is water (100 ml)
The product was extracted with chloroform (100 ml). The chloroform layer was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off. The resulting oily substance was purified by silica gel column chromatography (eluent: ethyl acetate) to obtain 1.2 g of the desired product. Melting point 43-46 [deg.] C.

(5) Synthesis of 5-methanesulfonyl-1-phenyl-1,2,4-triazole-3-carboxylic acid amide

[0040]

[Chemical 13]

1.2 g (5.1 mmol) of 5-methylthio-1-phenyl-1,2,4-triazole-3-carboxylic acid amide was dissolved in methylene chloride (20 ml),
At 10 ° C. or lower, 1.8 g (10 g of m-chloroperbenzoic acid
(mmol) was added in portions. After stirring at room temperature for 1.5 hours,
The precipitated solid was filtered off, and the filtrate was mixed with chloroform (50 m
l) was added, and the mixture was washed successively with saturated aqueous sodium carbonate solution and water. After drying over anhydrous sodium sulfate, the solvent was distilled off to obtain 1.0 g of the desired product. Melting point 155-160 [deg.] C.

(6) Synthesis of 2- (3-carbamoyl-1-phenyl-1,2,4-triazol-5-yloxy) acetic acid piperidide

[0043]

Embedded image

5-methanesulfonyl-1-phenyl-
1,2,4-triazole-3-carboxylic acid amide 0.
To a solution of 50 g (1.9 mmol) and 0.27 g (1.9 mmol) of glycolic acid piperidide in dimethyl sulfoxide (3 ml), 0.15 g of powdery potassium hydroxide.
(2.7 mmol) was added, and the mixture was stirred at room temperature for 0.5 hours. Add water (30 ml) and add chloroform (30 ml).
It was extracted twice with. The chloroform layer was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain 0.6 g of the desired product. Oily substance.

(7) 2- (3-cyano-1-phenyl-
Synthesis of 1,2,4-triazol-5-yloxy) acetic acid piperidide

[0046]

[Chemical 15]

2- (3-carbamoyl-1-phenyl-1,2,4-triazole-5-in THF (10 ml)
0.6 g (1.8 mmo)
l) and pyridine 0.3 g (3.8 mmol) are dissolved,
0.4 g of trifluoroacetic anhydride (1.9 mmo at 0 ° C.)
A solution of 1) in THF (3 ml) was added dropwise. 0.5 at room temperature
After stirring for an hour, water (30 ml) was added and chloroform (3
It was extracted twice with 0 ml). The chloroform layer was washed successively with 5% hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution, and dried over anhydrous sodium sulfate.
The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (eluent: chloroform) to obtain 0.25 g of the desired product. Oily substance. Example 4 (1) N-Methyl-N-phenyl-2- (3-carbamoyl-1-phenyl-1,2,4-triazole-5-
Iloxy) acetic acid amide synthesis

[0048]

[Chemical 16]

5-methanesulfonyl-1-phenyl-
1,2,4-triazole-3-carboxylic acid amide 0.
To a dimethyl sulfoxide (3 ml) solution of 50 g (1.9 mmol) and 0.31 g (1.9 mmol) of N-methyl-N-phenylglycolic acid amide, 0.15 g (2.7 mmol) of powdered potassium hydroxide was added. The mixture was stirred at room temperature for 0.25 hours. Water (30 ml) was added, and the mixture was extracted twice with chloroform (30 ml). The chloroform layer was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain 0.6 g of the desired product. Melting point 50-54 [deg.] C.

(2) N-methyl-N-phenyl-2-
Synthesis of (3-cyano-1-phenyl-1,2,4-triazol-5-yloxy) acetic acid amide

[0051]

[Chemical 17]

2- (3-carbamoyl-1-phenyl-1,2,4-triazole-5-in THF (10 ml)
0.6 g (1.7 mmo)
l) and pyridine 0.3 g (3.8 mmol) are dissolved,
0.4 g of trifluoroacetic anhydride (1.9 mmo at 0 ° C.)
A solution of 1) in THF (3 ml) was added dropwise. 0.5 at room temperature
After stirring for an hour, water (30 ml) was added and chloroform (3
It was extracted twice with 0 ml). The chloroform layer was washed successively with 5% hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution, and dried over anhydrous sodium sulfate.
The solvent was distilled off, and the obtained residue was purified by silica gel column chromatography (eluent: chloroform) to obtain 0.30 g of the desired product. Melting point 135-137 [deg.] C.

Next, examples of the compounds included in the present invention are shown in Tables 1 and 2 below including the compounds synthesized in the above Examples, but the compounds of the present invention are not limited thereto. However, the symbols in the table have the following meanings. Me: methyl group, Et: ethyl group, Pr-n: normal propyl group, Pr-iso: isopropyl group, Bu
-N: normal butyl group, Bu-iso: isobutyl group, Bu-sec: secondary butyl group, Bu-te
rt: tertiary butyl group, Pen-n: normal pentyl group, Hex-n: normal hexyl group, Pr-c
yc: cyclopropyl group, Bu-cyc: cyclobutyl group, Pen-cyc: cyclopentyl group, Hex-cy
c: cyclohexyl group, Ph: phenyl group

[Table 1]

[0055]

[Chemical 18]

[0056]

[Chemical 19]

[0057]

[Table 1] ────────────────────────────────── R ³ R ⁴ ───────── ────────────────────────── Me Me Me Et Me Pr-n Me Pr-iso Me Bu-n Me Bu-iso Me Bu-sec Me Bu-tert Me CHMeCHMe ₂ Me Pen-n Me Hex-n Me Hex-iso Me Pr-cyc Me Bu-cyc Me Pen-cyc Me Hex-cyc Me CH ₂ Pr-cyc Me CH ₂ Bu-cyc Me CH ₂ Pen-cyc Me CH ₂ Hex-cyc Me CH ₂ CH ₂ Pr-cyc Me CH ₂ CH = CH ₂ Me CH ₂ CH = CHMe ───────────────────── ──────────────

[0058]

[Table 2] [Continued Table 1] ────────────────────────────────── R ³ R ⁴ ── ──────────────────────────────── Me CH ₂ CH ₂ CH = CH ₂ Me CH ₂ C ≡ CH Me CH ₂ C≡C Me Me CH ₂ OMe Me CH ₂ OEt Me CH ₂ OPr-n Me CH ₂ OBu-n Me CH ₂ OBu-iso Me CH ₂ OBu-sec Me CH ₂ OBu-tert Me CH ₂ CH ₂ OMe Me CH ₂ CH ₂ OEt Me CH ₂ CH ₂ OPr-n Me CH ₂ CH ₂ CH ₂ OMe Me CH ₂ CH ₂ CH ₂ OEt Me CH ₂ CH ₂ CH ₂ CH ₂ OMe Me Ph Me 2-Cl-Ph Me 3-Cl- Ph Me 4-Cl-Ph Me 2,4-Cl ₂ -Ph Me 3,5-Cl ₂ -Ph ────────────────────────── ─────────

[0059]

[Table 3] [Continued Table 1] ────────────────────────────────── R ³ R ⁴ ── ──────────────────────────────── Me 2,6-Cl ₂ -Ph Me 2,3-Cl ₂ -Ph Me 2,5-Cl ₂ -Ph Me 2-F-Ph Me 3-F-Ph Me 4-F-Ph Me 2-F-4-Cl-Ph Me 2-Br-Ph Me 3-Br-Ph Me 4-Br-Ph Me 2-Me-Ph Me 3-Me-Ph Me 4-Me-Ph Me 2,4-Me ₂ -Ph Me 3,5-Me ₂ -Ph Me 2,6-Me ₂ -Ph Me 2,3-Me ₂ -Ph Me 2,5-Me ₂ -Ph Me 2-MeO-Ph Me 3-MeO-Ph Me 4-MeO-Ph Me 2-CF ₃ -Ph ─────── ────────────────────────────

[0060]

[Table 4] [Continued Table 1] ────────────────────────────────── R ³ R ⁴ ── ──────────────────────────────── Me 3-CF ₃ -Ph Me 4-CF ₃ -Ph Me 2,4 , 6-Cl ₃ -Ph Me 2,3,5-Cl ₃ -Ph Me 2,3,4-Cl ₃ -Ph Me 2-NO ₂ -Ph Me 2-CN-Ph Me CH ₂ Ph Me OMe Me OEt Me OPr-n Me OPr-iso Me OBu-n Me OBu-iso Me OBu-tert Me CH ₂ CH ₂ CN Me CH ₂ Ph Me CHMePh Me CMe ₂ Ph Me CH ₂ -2-Cl-Ph Me CH ₂ -3 -Cl-Ph Me CH ₂ -4-Cl-Ph ───────────────────────────────────

[0061]

[Table 5] [Continued Table 1] ────────────────────────────────── R ³ R ⁴ ── ──────────────────────────────── Me 2-Py Me 6-MeO-2-Py Me 6-Cl-2 -Py Me 6-F-2-Py Me 5-CF ₃ -2-Py Me 3-Cl-5-CF ₃ -2-Py Me 3-Py Me 4-Py Me CH ₂ -5-Cl-2- Py Me CH ₂ -6-Cl-3-Py Pr-i Ph Et Et Pr-n Pr-n Et Bu-n CH ₂ CH = CH ₂ CH ₂ CH = CH ₂ CH ₂ C≡CH CH ₂ C≡CH CH ₂ CH ₂ OMe CH ₂ CH ₂ OMe CH ₂ C ≡ CH OEt CH ₂ C ≡ CH OPr-n ─────────────────────────── ─────────

When R ³ and R ⁴ together with the nitrogen atom to which they are bonded form a saturated 3 to 9 membered ring.

[0063]

Embedded image

[0064]

[Chemical 21]

[Table 2]

[0066]

[Chemical formula 22]

[0067]

[Table 6] ──────────── ──────────── R ² R ² ──────────── ────── ────── H Me Et Pr-n Pr-iso Bu-n Bu-iso Bu-sec Bu-tert Pen-n Hex-n 2-Cl-Ph 3-Cl-Ph 4-Cl-Ph 2, 4-Cl ₂ -Ph 2-F-Ph 3-F-Ph 4-F-Ph 2-F-4-Cl-Ph 2-Br-Ph 3-Br-Ph 4-Br-Ph 2-Me-Ph 3-Me-Ph 4-Me-Ph 2,6-Me ₂ -Ph 2,4-Me ₂ -Ph 2-MeO-Ph 3-MeO-Ph 4-MeO-Ph 2-CF ₃ -Ph 3-CF ₃ -Ph 4-CF ₃ -Ph 3,5-Cl ₂ -Ph 2,6-Cl ₂ -Ph 2,3-Cl ₂ -Ph 2,4,6-Cl ₃ -Ph 2,3,5-Cl ₃ -Ph 2,3,4-Cl ₃ -Ph 2-Cl-4-CF ₃ -Ph 2,6-Cl ₂ -4-CF ₃ -Ph 2-NO ₂ -Ph 2-CN-Ph 3-CN -Ph 4-CN-Ph 2,5-Cl ₂ -Ph ──────────── ─────────────

[0068]

[Table 7] ──────────── ──────────── R ² R ² ──────────── ────── ────── 3,4-Cl ₂ -Ph 2,4- (NO ₂ ) ₂ -Ph 3-NO ₂ -Ph 4-NO ₂ -Ph 3-Py 4-Py 3-Cl-2-Py 4-Cl-2-Py 5-Cl-2-Py 6-Cl-2-Py 3-F-2-Py 4-F-2-Py 5-F-2-Py 6-F-2-Py 3 -Br-2-Py 4-Br-2-Py 5-Br-2-Py 6-Br-2-Py 3-CF ₃ -2-Py 4-CF ₃ -2-Py 5-CF ₃ -2- Py 6-CF ₃ -2-Py 3-Cl-5-CF ₃ -2-Py 3-Me-2-Py 4-Me-2-Py 5-Me-2-Py 6-Me-2-Py 3 -NO ₂ -2-Py 4-NO ₂ -2-Py 5-NO ₂ -2-Py 6-NO ₂ -2-Py ──────────── ──────── ─────

The application dose of the compound of the present invention varies depending on the application scene, application time, application method, target weeds, cultivated crops and the like, but generally, the amount of active ingredient is about 0.001 to 50 kg per hectare (ha), Preferably 0.01-10
About kg is appropriate. In addition, the compound of the present invention may be mixed with other types of herbicides, various insecticides, fungicides, plant growth regulators, synergists and the like, if necessary, during formulation or spraying.

In particular, when mixed with other herbicides, it can be expected to reduce the cost due to the reduction of the applied amount, to broaden the herbicidal spectrum due to the synergistic action of the mixed agents, and to have a higher herbicidal effect. At this time, it is possible to combine a plurality of known herbicides at the same time. The types of herbicides used in combination with the compound of the present invention include, for example, Farm Chemicals Handbook (Farm Chemicals Ha).
ndbook, 1990, and the like.

Examples of preferable agents to be used in combination with the compound of the present invention include pyrazosulfuron-ethyl (pyra
zosulfuron ethyl (generic name), bensulfuron methyl (generic name), cinosulfuron (ci)
nosulfuron / generic name, imazosulfu
ron / generic name). In addition to these, the following components can be further added.

Pretilachlor (generic name), esprocarb (generic name), pyrazolate (generic name), pyrazoxifene (py)
razoxyfen (generic name), benzophenap
/ Generic name), dymron / generic name, bromobutide / generic name, naproanilide (napr)
oanilide / generic name, clomeprop / generic name, CNP / generic name, clomethoxynil / chlome
thoxynil / generic name), bifenox / generic name, oxadiazon / generic name, mefenacet / generic name, butachlor
chlor / generic name), butenachlor / generic name, dithiopyr / generic name, benfuresate / generic name, pyributycarb
ributicarb / generic name), Bentocarb
/ Common name), dimepiperate (common name), molinate (molinate / common name), butamifos (common name), quinclorac (quinclorac)
/ Common name), cinmethrin (common name),
Simetrin (generic name), SAP (bensulide
/ Common name), dimethametryn (common name), MCPA, MCPB, 2 ', 3'-dichloro-4
-Ethoxymethoxybenzalinide (test name is HW-5
2), 1- (2-chlorobenzyl) -3- (α, α-dimethylbenzyl) urea (test name is JC-940), N-
[2 '-(3'-methoxy) -thienylmethyl] -N-
Chloroacetyl-2,6-dimethylanilide (test name is NSK-850) and the like can be mentioned.

When the compound of the present invention is applied as a herbicide, generally, a suitable carrier, for example, a solid carrier such as clay, talc, bentonite, diatomaceous earth or white carbon, or water, alcohols (isopropanol, butanol, benzyl alcohol, fluroalcohol) is used. Furyl alcohol etc.), aromatic hydrocarbons (toluene, xylene etc.), ethers (anisole etc.), ketones (cyclohexanone, isophorone etc.), esters (butyl acetate etc.), acid amides (N-methylpyrrolidone etc.) ) Or halogenated hydrocarbons (chlorobenzene etc.) and other liquid carriers can be mixed and applied, and if desired, surfactants, emulsifiers, dispersants, penetrants, spreading agents, thickeners, antifreeze. Agents, anti-caking agents, stabilizers, etc., liquids, emulsions, wettable powders,
It can be put into practical use in any dosage form such as a dry flowable agent, a flowable agent, a powder agent, and a granule agent.

Specific examples of herbicidal granules for paddy fields containing the compound of the present invention include solid bodies such as kaolinite, montmorillonite, diatomaceous earth, bentonite, talc, clay, calcium carbonate, calcium sulfate and ammonium sulfate. As the surfactant, alkylbenzene sulfonate, polyoxyethylene alkylaryl ether, lignin sulfonate, alkyl sulfosuccinate, polyoxyethylene fatty acid ester, naphthalene sulfonate, polyoxyethylene alkylaryl ether sulfate, alkylamine salt , Tripolyphosphate and the like. The content of these surfactants is not particularly limited, but is preferably in the range of 0.05 to 20 parts by weight with respect to 100 parts by weight of the granule of the present invention. Further, if necessary, a decomposition inhibitor such as epoxidized soybean oil may be contained in the granules of the present invention.

Next, formulation examples of preparations using the compound of the present invention will be shown concretely. However, the compounding examples of the present invention are not limited to these. In the following formulation examples, "part" means part by weight. [Wettable powder] Compound of the present invention ───────── 5 to 80 parts Solid carrier ───────── 10 to 85 parts Surfactant ────────── 1 10 parts Others ───────── 1-5 parts Other examples include anticaking agents.

[Emulsion] Compound of the present invention ───────── 1 to 30 parts Liquid carrier ───────── 30 to 95 parts Surfactant ───────── 5 to 15 parts [Flowable agent] Compound of the present invention ───────── 5 to 70 parts Liquid carrier ───────── 15 to 65 parts Surfactant ───────── -5 to 12 parts Others ───────── 5 to 30 parts Others include, for example, antifreezing agents and thickeners.

[Granular wettable powder (dry flowable agent)] Compound of the present invention ───────── 20 to 90 parts Solid carrier ───────── 10 to 60 parts Surfactant ── ──────── 1-20 parts [Granule] Compound of the present invention ───────── 0.1-10 parts Solid carrier ───────── 90-99.9 parts Others ───────── 1 to 5 parts [Formulation Example 1] Wettable powder Compound of the present invention No. 1 ─────────── 20 parts Dichlorite A ─────── ──── 76 parts (Kaolin-based clay: product name of Siglite Industrial Co., Ltd.) Solpol 5039 ─────────── 2 parts (Nonionic surfactant and anionic surfactant Mixture: Toho Chemical Industry Co., Ltd. product name Carplex (anti-caking agent) ────── 2 parts (White carbon: Shionogi Pharmaceutical Co., Ltd. ) Brand name) The above is uniformly mixed and pulverized to obtain a wettable powder.

[Formulation Example 2] Wettable powder Compound of the present invention No. 1 ─────────── 40 parts Dekrite A ─────────── 54 parts (kaolin clay : Siglite Co., Ltd. product name) Solpol 5039 ──────────── 2 parts (mixture of nonionic surfactant and anionic surfactant: Toho Chemical Industry Co., Ltd. product Name) Carplex (anti-caking agent) ──────── 4 parts (White carbon: Shionogi Pharmaceutical Co., Ltd. trade name) The above is uniformly mixed and pulverized to obtain a wettable powder.

[Formulation Example 3] Emulsion compound of the present invention No. 1 ─────────── 5 parts xylene ───────────75 parts dimethylformamide ───── ───── 15 parts Sorpol 2680 ──────────── 5 parts (mixture of nonionic surfactant and anionic surfactant: Toho Chemical Industry Co., Ltd. trade name) Are uniformly mixed to form an emulsion.

[Formulation Example 4] Flowable agent Compound of the present invention No. 1 ─────────── 25 parts Agrisol S-710───────── 10 parts (Nonionic surfactant Agent: Kao Corporation, trade name, Lunox 1000C ────────── 0.5 parts (anionic surfactant: Toho Chemical Industry Co., Ltd. trade name) 1% Rhodopol water ───── ─────── 20 parts (Thickener: Trade name of Loan Poulin Co., Ltd.) Water ─────────── 44.5 parts Mix the above uniformly to make a flowable agent.

[Formulation Example 5] Flowable agent Compound of the present invention No. 1 ─────────── 40 parts Agrisol S-710───────── 10 parts (Nonionic surfactant Agent: Kao Corporation, trade name, Lunox 1000C ────────── 0.5 parts (anionic surfactant: Toho Chemical Industry Co., Ltd. trade name) 1% Rhodopol water ───── ─────── 20 parts (Thickener: Trade name of Lorne Poulin Co., Ltd.) Water ─────────── 29.5 parts Mix the above uniformly to make a flowable agent.

[Formulation Example 6] Granular wettable powder (dry flowable agent) Compound of the present invention No. 1 ──────────── 75 parts Isoban No. 1 ──────────── -10 parts (anionic surfactant: Kuraray Isoprene Chemical Co., Ltd. trade name) Vanilex N ─────────── 5 parts (anionic surfactant: Sanyo Kokusaku Pulp Co., Ltd. trade name) Carplex # 80 ─────────── 10 parts (White carbon: Shionogi Pharmaceutical Co., Ltd. trade name) The above is uniformly mixed and pulverized to obtain a dry flowable agent.

[Formulation Example 7] Granules Compound of the present invention No. 1 ─────────── 1 part Bentonite ─────────── 55 parts Talc ────── ───── 44 parts After uniformly mixing and pulverizing the above, add a small amount of water, knead with stirring and kneading, granulate with an extrusion granulator, and dry to give granules.

[Formulation Example 8] Granules Compound of the present invention No. 1 ──────── 1.0 parts Compound (A) ─────── 0.07 parts DBSN ──────── 3 parts epoxidized soybean oil ─────── 1 part bentonite ─────── 30 parts talc ─────── 64.93 parts The above is uniformly mixed and pulverized, and a small amount of water is added. The mixture was kneaded, granulated with an extrusion granulator, granulated and dried to obtain granules.

The above-mentioned compound (A) is pyrazosulfuron ethyl (generic name), DBS
N means sodium dodecylbenzene sulfonate. When using, the above wettable powder, emulsion, flowable agent,
The granular wettable powder is diluted 50 to 1000 times with water and sprayed so that the active ingredient is 0.001 to 50 kg, preferably 0.01 to 10 kg per hectare (ha).

The compound of the present invention can be used as a herbicide for paddy fields in any treatment method such as soil treatment under flooded water and foliage treatment. For paddy weeds,
For example, Heraomodaka ( Alisma canaliculatum ), Omodaka ( Sagittaria trifolia ), Urikawa ( Sagittaria )
pygmaea ), etc.
Weeds, Cyperus difformis , Cyperus serotinus , Firefly ( Scirpus juncoid )
es), Cyperaceae (Cyperaceae) weeds typified by the water chestnut (Eleocharis kuroguwai), etc., false pimpernel (Li
ndemia pyxidaria )
thulariaceae) weeds, eels ( Monochoria vaginalis )
Wetgrass (Potenderiaceae) weeds represented by
Lythra (Lythra), typified by Potamogetonaceae weeds typified by Potamogeton distinctus and Rotala indica.
ceae) weeds, grass weeds (Gramineae) typified by Echinochloa crus-galli, and the like.

The compound of the present invention can be used as a herbicide for upland fields in any of the soil treatment, soil admixture treatment, and foliage treatment methods, and can be used in fields other than agricultural and horticultural fields such as paddy fields, upland fields and orchards. It can also be applied to control various weeds in non-agricultural land such as vacant land and track ends. Next, the usefulness of the compound of the present invention as a herbicide will be specifically described in the following test examples.

[Test Example 1] Herbicidal effect test by pretreatment for weed generation under flooded condition After alluvial soil was put into a 1/5000 are Wagner pot, water was added to mix it to obtain a fresh water condition with a depth of 4 cm.
The seeds of Nobie, Japanese eel, Cyperus japonicus, and Firefly were mixed and sown in the above pot, and then 2.5-leaf stage rice seedlings were transplanted. The pot was placed in a greenhouse at 25 to 30 ° C. to grow a plant, and on the first day after sowing, the compound of the present invention adjusted according to the formulation example was treated so as to have a predetermined dose on the water surface.
Three weeks after the treatment, the herbicidal effect on rice and various weeds was investigated. 0 is no effect and 5 is a 5-grade evaluation showing complete death. The results are shown in Table 3.

Test Example 2 Herbicidal Effect Test by Weeding Stage Treatment under Flooding Condition After alluvial soil was put into a 1/5000 are Wagner pot, water was added and mixed to obtain a fresh water condition with a water depth of 4 cm.
The seeds of Nobie, Japanese eel, Cyperus japonicus, and Firefly were mixed and sown in the above pot, and then 2.5-leaf stage rice seedlings were transplanted. The pots are placed in a greenhouse at 25 to 30 ° C. to grow plants, and 1 plant of Novier, eel, yellow cypress, firefly is used.
The compound of the present invention, which was prepared according to the formulation example, was treated so that when the rice reached to the 2-leaf stage and the 4-leaf stage of the rice, a predetermined dose was given to the water surface. Three weeks after the treatment, the herbicidal effect on rice and various weeds was investigated according to the criteria of Test Example 1. The results are shown in Table 4.

The symbols in each table have the following meanings. A
(Novier), B (firefly), C (seagrass), D (green grass), a (transplanted rice)

[0091]

[Table 8] [Table 3] ────────────────────────── Compound Compound Treatment dose A B C D a No. g / a ─ ───────────────────────── 1 2.5 5 5 5 5 5 0 2 10 5 5 5 5 5 0 3 3 2.5 5 5 5 5 5 0 4 2.5 5 5 5 4 0 ───────────────────────────

[0092]

[Table 9] [Table 4] ────────────────────────── Compound Treatment amount A B C D a No. g / a ─ ───────────────────────── 1 2.5 5 4 3 3 0 2 10 5 5 4 5 3 0 3 3 2.5 5 5 5 4 4 0 4 2.5 3 5 4 2 0 ───────────────────────────

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tsutomu Namaki 1470 Shiraoka, Shiraoka-cho, Minami-Saitama-gun, Saitama Nissan Biochemical Research Institute, Inc. (72) Inoue Kimihiro 1470 Shiraoka, Shiraoka-cho, Minami-Saitama-gun, Saitama 1470 Nissan Kagaku Kogyo Co., Ltd.Biological Sciences Research Institute (72) Inventor Shigeomi Watanabe 1470 Shiraoka, Shiraoka-cho, Minami Saitama-gun, Saitama Prefecture Nissan Kagaku Kogyo Co., Ltd. Biological Sciences Research Institute (72) Kenichi Shiojima, Shirooka-cho, Minami Saitama-gun Saitama 1470 Shiraoka Nissan Kagaku Kogyo Co., Ltd. Bioscience Research Institute (72) Inventor Kunimitsu Nakahira 1470 Shiraoka, Shiraoka-cho, Minamisaitama-gun, Saitama Pref.

Claims (2)

[Claims] 1. Formula (1):[In the formula, R¹Is a hydrogen atom, cyano group, nitro group, carba
Represents a moyl group or a halogen atom, R²Is C_1-6Alkyl group, phenyl group (C_1-4Alkyl
Group, C_1-4Haloalkyl group, C_1-4Alkoxy group, shea
Group selected from the group consisting of nitro group, nitro group and halogen atom
May be substituted with two or more substituents. ),
Pyridyl group (C _1-4Alkyl group, C_1-4Haloalkyl
Group, C_1-4Alkoxy, cyano, nitro and ha
Depending on one or more substituents selected from the rogen atom
May be replaced. ), R³And R^FourAre each independently a hydrogen atom, C_1-6A
Rukiru group, C_3-6Cycloalkyl group, C_2-4Alkenyl
Group, C_2-4Alkynyl group, C_3-6Cycloalkyl group
Converted C_1-2Alkyl group, C_1-4Alkoxy C_1-4A
Rukyl group, phenyl group (C_1-4Alkyl group, C_1-4Halo
Alkyl group, C_1-4Alkoxy group, cyano group, nitro group
And one or more substitutions selected from halogen atoms
It may be substituted by a group. ) Is replaced by
C_1-4Alkyl group, phenyl group (C_1-4An alkyl group,
C_1-4Haloalkyl group, C_1-4Alkoxy group, cyano
A group selected from a group, a nitro group and a halogen atom, or
It may be substituted with two or more substituents. ),
Lysyl group (C_1-4Alkyl group, C_1-4A haloalkyl group,
C_1-4Alkoxy, cyano, nitro and halogen
Position by one or more substituents selected from
It may be replaced. ) Replaced by C _1-4Al
Kill group, pyridyl group (C_1-4Alkyl group, C_1-4Haloa
Rukiru group, C_{1- Four}Alkoxy group, cyano group, nitro group
And one or more substituents selected from halogen atoms
May be replaced by ), C_1-4Alkoxy
Group (however, R^FourAnd R^FiveAnd at the same time represent an alkoxy group
There is no. ) Or cyano C_1-4Represents an alkyl group. However
Then R^FourAnd R^FiveIs 3 together with the attached nitrogen atom
~ 9-membered ring may be constituted, oxygen atom, sulfur source in the ring
Child, nitrogen atom, carbonyl group, sulfonyl group or
It may contain one or more saturated bonds, and the ring is C
_1-4Alkyl group, C_1-4Alkoxy group, hydroxyl group, halogen
Atom, C_1-4Haloalkyl group, C_1-4Alkoxycar
Substituted by a carbonyl group, a phenyl group or a benzyl group
The ring may be C_1-4Crosslinked by alkylene
Optionally, the ring is fused with a benzene ring
May be. ] Triazole glycolic acid
Mid derivative. 2. A herbicide containing, as an active ingredient, one or more of the compounds according to claim 1.