JPH04235971A - Substituted aminosulfonamide and herbicide - Google Patents

Abstract

PURPOSE:To provide a substituted aminosulfonamide derivative or an agricultur ally suitable salt thereof having a strong herbicidal force against many weeds and high safety for wheat, soybeans, etc., and useful as a herbicide. CONSTITUTION:A compound of formula I [Q is a group of formula II, III or IV (R1 is H, 1-6C alkyl, 3-7C cycloalkyl, etc.; R2 is 1-6C alkyl, 2-6C alkenyl, 2-6C alkinyl, etc.,); X is O, S; G is a group of formula V (a, b, c, d are H, 1-6C alkyl, 2-6C alkenyl, etc.)]. The compound of formula I is produced e.g. by dissolving a substituted aminosulfonyliso(thio)cyanate derivative in a sufficiently dry inert solvent such as dioxane or acetonitrile and subsequently adding a pyrazoline derivative of formula VII to the solution with stirring. When the reaction is difficult to proceed, a fine amount of triethylamine, etc., is preferably added to the mixture.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to novel substituted aminosulfonamide derivatives, their agriculturally suitable salts, and herbicides containing these compounds as active ingredients. BACKGROUND OF THE INVENTION It is essential to use herbicides to protect important crops such as rice, wheat, corn, soybeans, cotton, and beets from weed damage and increase yields. Particularly in recent years, there has been a demand for selective herbicides that can selectively kill only weeds without causing chemical damage to crops even when applied to the foliage of crops and weeds simultaneously in cultivated land where these useful crops and weeds coexist. ing. In addition, from the viewpoint of preventing environmental pollution and reducing economic costs during transportation and spraying, search research has been carried out for many years to find compounds that have a high herbicidal effect with as low a dose as possible. Although some compounds with these properties are currently used as selective herbicides, there is still a need for new compounds with these properties. As a prior art with a structure similar to the compound of the present invention, N-
Alkoxy- and N-alkylsulfonylaminosulfonylureas are described in JP-A-60-48973 and 1
-Carbamoyl-2-pyrazoline is JP-A-63-122
Although disclosed in Japanese Patent No. 671, substituted aminosulfonamide derivatives having a pyrazoline structure, such as the compound of the present invention, have not been previously known at all and are novel compounds. [Means for Solving the Problems] In order to develop herbicides that are selective for important crops, the present inventors have continued their research over many years to develop compounds with higher herbicidal power and selectivity. We have investigated the herbicidal properties of many compounds. As a result, the formula (1) [Chemical formula 4] [wherein Q represents [Chemical formula 5], R1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, Alkyl group having 1 to 6 carbon atoms substituted with cycloalkyl group having 3 to 7 carbon atoms, alkenyl group having 2 to 6 carbon atoms, alkynyl group having 2 to 6 carbon atoms, 1 to 6 carbon atoms an alkyl group having 1 to 6 carbon atoms substituted with an alkoxy group having 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted by a mono- or polyhalogenoalkoxy group having 1 to 6 carbon atoms, a carbon atom an alkyl group having 1 to 6 carbon atoms substituted with an alkylthio group having 1 to 6 carbon atoms; an alkyl group having 1 to 6 carbon atoms substituted by an alkylsulfonyl group having 1 to 6 carbon atoms; C1-6 mono- or polyhalogenoalkyl group, C1-6 alkyl group substituted with cyano group, C1-6 alkoxycarbonyl group substituted with C1-6 alkoxycarbonyl group; an alkyl group having 1 to 6 carbon atoms substituted with an alkylcarbonyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group (however, these phenyl groups and benzyl groups are substituted with halogen atoms, trifluoro Substituted with one or more substituents selected from a methyl group, a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alkoxycarbonyl group having 1 to 6 carbon atoms. ), and R2 has 1 to 6 carbon atoms.
an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with an alkoxy group having 1 to 6 carbon atoms, a carbon atom An alkyl group having 1 to 6 carbon atoms substituted with an alkylthio group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted by an alkoxycarbonyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms substituted with an alkylthio group having 1 to 6 carbon atoms; 1-6 mono- or polyhalogenoalkyl group, 1-6 carbon atoms
an alkyl group having 1 to 6 carbon atoms substituted with an alkylsulfonyl group, a phenyl group or a benzyl group (
However, these phenyl groups and benzyl groups are selected from halogen atoms, trifluoromethyl groups, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and alkoxycarbonyl groups having 1 to 6 carbon atoms. may be substituted with one or more substituents. ), X represents an oxygen atom or a sulfur atom, and G represents [Chemical formula 6
] A, b, c and d each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or a halogen C1 to C6 alkyl groups mono- or polysubstituted by atoms, C1 to C6 alkoxy groups, C1 to C6 alkyl groups substituted by C1 to C6 alkoxy groups; , an alkoxycarbonyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted by an alkylthio group having 1 to 6 carbon atoms, a carbon substituted by an alkylsulfonyl group having 1 to 6 carbon atoms Alkyl group having 1 to 6 atoms, alkylthio group having 1 to 6 carbon atoms, alkylcarbonyl group having 1 to 6 carbon atoms, cycloalkyl group having 3 to 7 carbon atoms, cycloalkenyl having 3 to 7 carbon atoms group, cyano group, phenyl group or benzyl group (however, these phenyl and benzyl groups are halogen atoms, trifluoromethyl groups, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, carbon may be substituted with one or more substituents selected from an alkoxycarbonyl group having 1 to 6 atoms and a nitro group), a 5- or 6-membered heterocycle (however, these heterocycles may be substituted with a nitrogen atom , contains 1 to 3 heteroatoms selected from oxygen atoms and sulfur atoms in the ring.Also, contains a sulfonyl group.In addition, these heterocycles include an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms,
6 alkoxy group, a halogen atom, a trifluoromethyl group, a nitro group, and an alkoxycarbonyl group having 1 to 6 carbon atoms. ), naphthyl group, benzene-fused heterocycle (however, these benzene-fused heterocycles contain 1 to 2 heteroatoms selected from nitrogen atoms, oxygen atoms, and sulfur atoms in the ring. , alkyl group having 1 to 6 carbon atoms, 1 carbon atom
It may be substituted with one or more substituents selected from -6 alkoxy groups, halogen atoms, trifluoromethyl groups, nitro groups, and alkoxycarbonyl groups having 1 to 6 carbon atoms. ) represents. ] and their agriculturally suitable salts (hereinafter referred to as compounds of the present invention) are extremely effective against many weeds in both soil and foliage treatments. The present invention was completed by discovering that it has strong herbicidal power and is highly safe for important crops such as wheat, corn, cotton, soybeans, beets, and rice. On the other hand, since the compounds of the present invention exhibit high herbicidal activity at a much lower dose than conventional herbicides, they are also useful as herbicides for orchards and non-agricultural lands. The compound of the present invention represented by formula (1) can be easily produced by selecting any one of Reaction Formulas 1 to 4 below. Reaction formula 1 [Chemical formula 7] [In the formula, Q, G and X represent the same meanings as above. ]
That is, the substituted aminosulfonyl iso(thio)cyanate derivative (2) is dissolved in a sufficiently dried inert solvent such as dioxane, acetonitrile, acetone, etc., and the pyrazoline derivative represented by formula (3) is added thereto and stirred. By doing so, the compound (1) of the present invention is generally obtained by rapidly reacting. If the reaction is difficult to proceed, the reaction can be facilitated by adding a small amount of a suitable base such as triethylamine, triethylenediamine, pyridine, sodium alkoxide, sodium hydride, potassium carbonate, etc. Reaction formula 2 [Image Omitted] [In the formula, Q, G and X have the same meanings as above. Y
represents an alkyl group having 1 to 6 carbon atoms or a phenyl group. ] That is, substituted aminosulfonamide derivatives (
Compound (5) is obtained by reacting 4) with chloroformic acid (thio)ester or carbonic acid (thio)ester in a solvent such as acetone, methyl ethyl ketone, or acetonitrile in the presence of a base such as potassium carbonate. The compound (1) of the present invention can then be obtained by heating the compound (3) with the compound (3) in a solvent such as toluene. Reaction formula 3 [Chemical formula 9] [In the formula, Q, G and Y have the same meanings as above. ] That is, the reaction between substituted amines (7) and phenyl N-chlorosulfonyl carbamate (6 ; Y = phenyl group) or alkyl N-chlorosulfonyl carbamate (6 ; Y = alkyl group having 1 to 6 carbon atoms) is , substituted amines (7) phenyl per mole
The reaction is carried out using 0.5 to 3.0 molar amount of N-chlorosulfonyl carbamate (6; Y=phenyl group) or alkyl N-chlorosulfonyl carbamate (6; Y=alkyl group having 1 to 6 carbon atoms). Preferably, a range of 0.9 to 1.2 molar amounts is suitable. The reaction temperature can be arbitrarily selected from the range of -50°C to 100°C, but preferably the range of -20°C to 30°C. This reaction is carried out using various bases. The amount of base is 0.5 per mole of substituted amine (7)
4.0 molar amount is used. Suitable bases include, for example, metal hydrides such as sodium hydride, metal alkoxides such as sodium ethoxide, alkyl metals such as n-butyllithium, triethylamine, pyridine, 1,8-diazabicyclo [5.4. 0] -7-
Organic bases such as undecene (DBU) and inorganic bases such as potassium hydroxide and sodium hydroxide are used. Particularly preferred is the use of metal hydrides. Suitable solvents for this reaction include solvents inert to this reaction, such as benzene, toluene, aromatic hydrocarbons such as xylene, halogenated hydrocarbons such as dichloromethane, chloroform, and carbon tetrachloride, ethyl ether, isopropyl ether, Ethers such as dioxane and tetrahydrofuran, nitrites such as acetonitrile and propionitrile, hydrocarbons such as petroleum ether, petroleum benzene and hexane, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, dimethylformamide and dimethylacetamide. , amides such as hexamethylphosphoric triamide. These solvents may be used alone or in combination. Particularly preferred is the use of ethers or amides. Next, phenyl N-substituted aminosulfonyl carbamate (5; X=O, Y=phenyl group) or alkyl N-substituted aminosulfonyl carbamate (5; X=O, Y=alkyl group having 1 to 6 carbon atoms) and the compound Compound (1) of the present invention can be obtained by heating (3) in a solvent such as benzene or toluene. Reaction formula 4 [In the formula, Q, G and Y have the same meanings as above. ]
That is, the substituted aminosulfonamide derivative (4) is dissolved in a solvent such as acetone, acetonitrile, dioxane, etc.
Inorganic bases such as potassium carbonate or triethylamine,
In the presence of an organic base such as DBU, carbamate derivatives (
Compound (1) of the present invention can be obtained by reacting with (8). Substituted aminosulfonyl iso(thio)cyanate derivative (2) as a raw material used in reaction formula 1
is from substituted amines (7), according to JP-A-2-45473
From the method described in JP-A No. 49-81320, etc., or from the substituted aminosulfonamide derivative (4), European Patent Application Publication No. 87,
It can be synthesized by referring to the methods described in JP-A No. 780, JP-A-55-13266, and the like. Also,
The substituted aminosulfonamide derivative (4) can be synthesized from the substituted amine (7) using the methods shown in Reaction Formulas 5 and 6 below. Reaction formula 5 [Chemical formula 11] [In the formula, Q has the same meaning as above. ] In Reaction Scheme 5, the tert-butyl group is removed using trifluoroacetic acid. The amount of trifluoroacetic acid can be arbitrarily selected from equimolar to excess. There is no problem in using trifluoroacetic acid as a solvent. The reaction temperature is -
The temperature can be arbitrarily selected from the range of 50°C to 80°C. Preferably, the temperature range is from -20°C to 30°C. When using a solvent in this reaction, a solvent inert to this reaction, such as benzene, toluene, xylene-based aromatic hydrocarbons,
Halogenated hydrocarbons such as dichloromethane, chloroform, and carbon tetrachloride; ethers such as ethyl ether, isopropyl ether, dioxane, and tetrahydrofuran; nitrites such as acetonitrile and propionitrile; hydrocarbons such as petroleum ether, petroleum benzyl, and hexane; These include ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, and amides such as dimethylformamide, dimethylacetamide, and hexamethylphosphoric triamide. These solvents may be used alone or in combination. Reaction formula 6 [Chemical formula 12] (In the formula, Q has the same meaning as above.) In reaction formula 6, the reaction between t-butanol and chlorosulfonyl isocyanate is carried out by a method known per se, for example, JP-A-Sho. 50
This can be carried out with reference to Japanese Patent No.-101323. The reaction between substituted amines (7) and tert-butylsulfamoyl chloride is performed using 0 tert-butylsulfamoyl chloride per mole of substituted amines (7).
．． 5 to 3.0 molar amounts are used. Preferably, a range of 0.9 to 1.2 molar amounts is suitable. The reaction temperature can be arbitrarily selected from the range of -50°C to 100°C, but preferably the range of -20°C to 30°C. This reaction is carried out using various bases. The amount of base is 0.5 per 1 mole of substituted amines (7).
~4.0 molar amounts are used. Preferably, a range of 0.8 to 2.2 molar amounts is suitable. Suitable bases include, for example, metal hydrides such as sodium hydride, metal alkoxides such as sodium ethoxide, alkyl metals such as n-butyllithium, organic bases such as triethylamine, pyridine, and DBU, and potassium hydroxide. Inorganic bases such as , sodium hydroxide and the like are used. Particularly preferred is the use of metal hydrides. Suitable solvents for this reaction include solvents inert to this reaction, such as benzene, toluene, aromatic hydrocarbons such as xylene, halogenated hydrocarbons such as dichloromethane, chloroform, and carbon tetrachloride, ethyl ether, isopropyl ether, Ethers such as dioxane and tetrahydrofuran, nitrites such as acetonitrile and propionitrile, hydrocarbons such as petroleum ether, petroleum benzene and hexane, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, dimethylformamide and dimethylacetamide. , amides such as hexamethylphosphoric triamide. These solvents may be used alone or in combination. Particularly preferred is the case where ethers or amides are used. In reaction formula 3, phenyl N-chlorosulfonylcarbamate (6; Y=phenyl group) or alkyl N-chlorosulfonylcarbamate (
6; Y=alkyl group) can be prepared by a method known per se, for example, by Chemische Beri
Synthesis can be carried out with reference to Vol. 96, p. 56 (1963). The substituted amines (7) used as starting materials for the above reaction are known or can be easily synthesized by generally known methods. Furthermore, the pyrazolines (3) used as starting materials for the above reaction can be easily synthesized with reference to Japanese Patent Application Laid-Open No. 122671/1983. Synthesis examples of the compounds of the present invention will be specifically described below as examples, but the present invention is not limited thereto. [Example] Example 1 1-[(N-methanesulfonyl-N-methylamino)sulfonylcarbamoyl]-3-methyl-5-phenyl-
Synthesis of 2-pyrazoline [Chemical 13] 3-methyl-5-phenyl-2-pyrazoline 0.48 g
(3 mmol) was dissolved in 10 ml of dry dichloromethane, and 0.96 g (4.5 mmol) of N-methanesulfonyl-N-methylaminosulfonyl isocyanate was prepared at room temperature.
was dripped. After stirring the reaction mixture at room temperature for 15 hours, dichloromethane was distilled off under reduced pressure. Diethyl ether was added to the residue, and the precipitated crystals were filtered off. The crystals were thoroughly washed with diethyl ether and dried to obtain 0.95 g of the desired 1-[(N-methanesulfonyl-N-methyl-amino)sulfonylcarbamoyl]-3-methyl-5-phenyl-2-pyrazoline. Ta. Melting point: 137-139°C Example 2 Synthesis of 1-[(N-methanesulfonyl-N-ethylamino)sulfonylcarbamoyl]-3,5-dimethyl-5-phenyl-2-pyrazoline [Formula 14] 60% sodium hydride 6.15 g (50 mmol) of N-ethyl methanesulfonamide dissolved in 10 ml of dry THF was added to 100 ml of dry tetrahydrofuran (THF) containing 4 g (100 mmol) under ice cooling, and the temperature was gradually raised to room temperature, and then continued at the same temperature. Stirred for 15 hours. Next, 50 ml of dry THF containing 13.0 g (55 mmol) of phenyl N-chlorosulfonyl carbamate was added.
was added dropwise under ice-cooling, the temperature was gradually raised to room temperature, and the mixture was subsequently stirred at room temperature for 3 hours. Add 10.4 g of 35% hydrochloric acid to the reaction mixture.
The reaction product was poured into 700 ml of ice water containing (100 mmol), and the reaction product was extracted with diethyl ether. The diethyl ether layer was washed successively with water and saturated brine, then dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. Add a mixed solvent of diethyl ether and n-hexane to the residue,
The precipitated crystals were filtered off. Crystals with diethyl ether
- After washing with a mixed solvent of hexane and drying, phenyl N-[(N-methanesulfonyl-N-
8.0 g of ethyl-amino)sulfonyl]carbamate were obtained. Melting point 125-127°C Next, 0.97 g (3 mmol) of the above compound, 3,5-
1.57 g of dimethyl-5-phenyl-2-pyrazoline (
A mixture of 9 mmol) and 30 ml of dry benzene was heated to reflux for 5 minutes. After cooling, 100 ml of ethyl acetate was added, and the ethyl acetate layer was washed three times with dilute hydrochloric acid and then twice with water. Next, after drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The obtained residue was washed with n-hexane and diethyl ether in this order, and the precipitated crystals were filtered off. The crystals were washed with diethyl ether and dried to obtain the desired 1-
0.7 g of [(N-methanesulfonyl-N-ethyl-amino)sulfonylcarbamoyl]-3,5-dimethyl-5-phenyl-2-pyrazosone was obtained. Melting point 124-125°C Example 3 1-[(N-methanesulfonyl-N-ethoxyamino)
Synthesis of sulfonylcarbamoyl]-3-methyl-5-phenyl-2-pyrazoline [Synthesis 15] 5.0 g (51.2 mmol) of ethoxyamine hydrochloride was dissolved in 20 ml of pyridine, and while cooling on ice, methanesulfonyl chloride 5. 87 g (51.2 mmol) was added dropwise. The reaction mixture was heated to room temperature and stirred for 20 hours. Next, 300 ml of benzene was added, the precipitated pyridine hydrochloride was filtered off, and the filtrate was distilled off under reduced pressure. 100 ml of chloroform was added to the residue, washed twice with 50 ml of 5% hydrochloric acid and twice with 50 ml of water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained pale yellow oil was distilled under reduced pressure (boiling point: 90-92°C/0.4 mmHg) to obtain 5.0 g of N-ethoxymethanesulfonamide as colorless crystals with a melting point of 54-55°C. Next, sodium hydride 1
．． 23g (51.3mmol) and 100ml of dry THF
Add N-ethoxymethanesulfonamide 3. under ice cooling.
4 g (24.5 mmol) was added dropwise. The reaction mixture was heated to room temperature and stirred for 20 hours. The reaction mixture was then cooled on ice, and 5.77 g (24.5 mmol) of phenyl N-chlorosulfonyl carbamate was added to THF2.
The solution was dissolved in 0 ml and added dropwise. The temperature was then raised to room temperature, and the mixture was stirred at room temperature for 4 hours. The reaction mixture was mixed with 500 ml of ice water containing 5.3 g of 35% hydrochloric acid.
and extracted three times with 100 ml of ether. The extract was washed three times with 100 ml of water and once with 100 ml of saturated brine, dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. 6.12 g of phenyl N-(N-ethoxy-N-methanesulfonylamino)sulfonyl carbamate was obtained as a pale yellow oil. Next, this carbamate 1.
0.56 g (3 mmol) of 3-methyl-5-phenyl-2-pyrazoline was dissolved in 30 ml of dry benzene.
g (3.5 mmol) was added thereto, and the mixture was heated under reflux at 100° C. for 5 minutes. After cooling, the solvent was distilled off under reduced pressure, and the residue was subjected to reverse phase column chromatography (acetonitrile:water = 3:1
) to obtain 1-[(N-methanesulfonyl-N-ethoxyamino)sulfonylcarbamoyl]-3-methyl-5-phenyl-2-pyrazoline with a melting point of 135-136.
Obtained as pale yellow crystals at ℃. Example 4 Synthesis of 1-[(N-methoxy-N-methylamino)sulfonylcarbamoyl]-3-methyl-5-phenyl-2-pyrazoline [Formula 16] N,O-dimethylhydroxylamine hydrochloride 2.44 g
(25 mmol) was suspended in 200 ml of dichloromethane, and 5.06 g (50 mmol) of triethylamine was added. While cooling on ice, 5.89 g (25 mmol) of phenyl N-chlorosulfonyl carbamate was dissolved in 20 ml of dichloromethane and added dropwise. The reaction mixture was heated to room temperature and stirred for 1 hour. The precipitated crystals were filtered off, and the filtrate was washed twice with 50 ml of 5% hydrochloric acid and twice with 50 ml of water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. Phenyl N-(N-methoxy-N
6.0 g of -methylamino)sulfonyl carbamate were obtained as a colorless oil. Next, this carbamate 2.08
g (8 mmol) was dissolved in 30 ml of benzene, and 1.6 g (10 mmol) of 3-methyl-5-phenyl-2-pyrazoline was dissolved.
mol) was added thereto, and the mixture was heated under reflux at 100°C for 5 minutes. After cooling, the solvent was distilled off under reduced pressure, and the residue was washed with a mixed solution of n-hexane and ether to obtain the desired 1-[(N-methoxy-N-methylamino)sulfonylcarbamoyl]-3-
Methyl-5-phenyl-2-pyrazoline with a melting point of 96-9
Obtained as colorless crystals at 7°C. The structural formulas and physical properties of compounds synthesized using the same method as in Examples 1 and 2 are shown below. [Chemical 17] [Chemical 18] [Chemical 19] [Chemical 20] [Chemical 21] [Chemical 22] Next, examples of the compounds included in the present invention, including the compounds synthesized in the above Examples, are shown in the following The compounds of the present invention are shown in Table 6, but 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-i: isopropyl group, c-Pr: cyclopropyl group, Bun-n: normal butyl group, Bu-sec: secondary butyl group, But-t: tertiary butyl group,
Pen-n; normal pentyl group, Hex-n; normal hexyl group, c-Pen; cyclopentyl group,
c-Hex: cyclohexyl group, Ph: phenyl group, Gn has the same meaning as G above, and the following Ga, G
b and Gc. Ga=G1 to G479 (i.e., G1 to G479
It means any of the following. ) Gb=G1 to G72 and G102 to G136 (that is, it means both G1 to G72 and G102 to G136) Gc=G1 to G35 and G1
02 to G136 (i.e. G1 to G35 and G
102 to G136. ) [chemical 2
3] [Formula 24] [Formula 25] [Formula 26] [Formula 27] [Formula 28] [Formula 29] [Formula 30] [Formula 31] [Formula 32] [Formula 33] [Formula 34] [Formula 35] [Formula 36] [Formula 37] [Formula 38] [Formula 39] [Formula 40] [Formula 41] [Formula 42] [Formula 43] [Formula 44] [Formula 45] [Formula 46] [Formula 47] [Formula 47] 48] [Chemical 49] [Chemical 50] [Chemical 51] [Chemical 52] [Chemical 53] [Chemical 54] [Chemical 55] [Chemical 56] [Chemical 57] [Chemical 58] [Chemical 59] [Chemical 60] [Chemical 61] [Chemical 62] [Chemical 63] [Chemical 64] [Chemical 65] [Chemical 66] [Chemical 67] [Chemical 68] [Chemical 69] [Chemical 70] [Chemical 71] [Chemical 72] [Chemical 73] [Chemical 74] [Chemical 75] [Chemical 76] [Chemical 77] [Chemical 78] [Chemical 79] [Chemical 80] [Chemical 81] [Chemical 82] [Chemical 83] [Chemical 84] [Chemical 85] [Formula 86] [Formula 87] [Formula 88] [Formula 89] [Formula 90] [Formula 91] [Formula 92] [Formula 93] [Formula 94] [Formula 95] [Formula 96] [Formula 97] [Chemical formula 99] [Chemical formula 100] Table 1 [Chemical formula 101] [0001] [0002] [0003] [0004] [0005] [0006] [0007] [00008] [0009] [0010] 0011] [0012] [0013] [0014] [0015] [0016] R1 R2
Gn──────────────────────
── 0018 0019 0020 0021 0022 0023 0024 0025 0026 0027 0029 0030 0031 0032 [0034] [0035] [0036] [0037] [0038] [0039] [0040] [0041] [0042] [0043] [00044] [0045] [0046] [0047] [0048] [0049] ] [0050] [0053] [0054] [0055] [0056] [0057] [0058] [0059] [0060] [0061] [0062] [0063] [0064] [0065] [0066] [0067] [0068] [0070] [0071] [0072] [0073] [0074] [0075] [0076] [0077] [0078] [00079] [0080] [0081] [0082] [0083] [0084] [0085] [0086] [0087] [0089] [0090] [0091] [0092] [0093] [0094] [0095] [00096] [0097] [0098] [0099] [0100] 0101 ] [0102] [0103] [0104] [0105] [0106] [0107] [0108] [0109] [0110] [0111] [0112] [0113] [0114] [0115] [0116] [0117] [0118] [0120] The compounds of the present invention can be applied to control various weeds not only in agricultural and horticultural fields such as fields, paddy fields, and orchards, but also in non-agricultural lands such as playgrounds, vacant lots, and railway edges. The amount of the applied drug varies depending on the application situation, application time, application method, target weeds, cultivated crops, etc., but in general, the amount of active ingredient is 0.0001 to 10 kg per hectare (ha).
A suitable amount is preferably about 0.005 to 5 kg. Furthermore, the compound of the present invention may be applied in combination with other herbicides, various insecticides, fungicides, plant growth regulators, synergists, etc. at the time of formulation or spraying, if necessary. In particular, by applying it in combination with other herbicides, it can be expected to reduce costs by reducing the amount of applied chemicals, expand the herbicidal spectrum due to the synergistic effect of the mixed chemicals, and achieve higher herbicidal effects. On this occasion,
Combination with multiple known herbicides at the same time is also possible. The types of herbicides to be mixed with the compound of the present invention include, for example, the Farm Chemicals Handbook (Far
m Chemicals Handbook) 199
There are compounds listed in the 0th edition. When applying the compound of the present invention as a herbicide, a suitable carrier is generally used, such as a solid carrier such as clay, talc, bentonite, diatomaceous earth, white carbon, water, alcohols (isopropanol, butanol, benzyl alcohol, furfuryl 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.). is possible,
If desired, surfactants, emulsifiers, dispersants, penetrants, spreading agents, thickeners, antifreeze agents, anticaking agents, stabilizers, etc. may be added to produce solutions, emulsions, hydrating agents, dry flowable agents, etc. It can be put to practical use in any form such as a flowable agent, powder, or granule. Next, specific formulation examples of formulations using the compounds of the present invention will be shown. However, the formulation examples of the present invention are not limited to these only. In addition, in the following formulation examples, "parts" mean parts by weight. [Wettable powder] Compound of the present invention ──────── 5 to 80 parts Solid carrier
────────10-85 parts surfactant ──
───── Parts 1 to 10 and others ────
--- 1 to 5 parts Other examples include anti-caking agents. [Emulsion] Compound of the present invention 1 to 30 parts liquid carrier
────────30-95 parts surfactant ──
────── 5 to 15 parts [Flowable agent] Compound of the present invention ────── 5 to 70 parts Liquid carrier
────────15-65 parts surfactant ──
────── Parts 5 to 12 and others ────
--- 5 to 30 parts Other examples include antifreeze agents, thickeners, and the like. [Granular hydrating agent (dry flowable agent)] Compound of the present invention─
──────20-90 parts solid carrier ──────
──10-60 parts surfactant ──────── 1
~20 parts [granules] Compound of the present invention---------0.1~10 parts Solid carrier---------90~99.99 parts Others
──────── Part 1-5 [0122
] [Formulation Example 1] Wettable powder Compound of the present invention No. 1 ────────20 parts Sieglite A ────────76 parts (
Kaolin clay: Sieglite Industries Co., Ltd. (Product name) Solpol 5039 ──────── 2
1 part (mixture of nonionic surfactant and anionic surfactant: Toho Chemical Co., Ltd. trade name) Carplex (anti-caking agent) 2 parts (white carbon: Shionogi & Co., Ltd.) ) Product name) The above is mixed and ground uniformly to make a wettable powder. [Formulation Example 2] Hydrating agent Compound of the present invention No. 2 ────────40 parts Sieglite A ────────54 parts (
Kaolin clay: Sieglite Industries Co., Ltd. (Product name) Solpol 5039 ──────── 2
Part (mixture of nonionic surfactant and anionic surfactant: Toho Chemical Co., Ltd. trade name) Carplex (anti-caking agent) --- 4 parts (White carbon: Shionogi & Co., Ltd.) ) Product name) The above is mixed and ground uniformly to make a wettable powder. [Formulation Example 3] Emulsion Invention Compound No. 3 ──────── 5
Part xylene ────────
75 parts dimethylformamide ──────── 15 parts Solpol 2680 ──────── 5
(Mixture of nonionic surfactant and anionic surfactant: Toho Chemical Industry Co., Ltd. trade name) The above is uniformly mixed to form an emulsion. [Formulation Example 4] Flowable agent of the present invention compound No. 5 ────────25 parts Agrisol S-710 ────────10 parts (nonionic surfactant: Kao Corporation trade name) Lunox
1000 C ──────── 0.5 parts (Anionic surfactant: Toho Chemical Industry Co., Ltd. trade name) 1% Rhodopol water ──────── 20 parts (Thickener: Lawn・Poulenc product name) Water
────────44.5 parts or more are mixed uniformly to form a flowable agent. [Formulation Example 5] Flowable Agent Invention Compound No. 6 ────────40 parts Agrisol S-710 ────────10 parts (nonionic surfactant: Kao Corporation trade name) Lunox
1000 C ──────── 0.5 parts (Anionic surfactant: Toho Chemical Industry Co., Ltd. trade name) 1% Rhodopol water ──────── 20 parts (Thickener: Lawn・Poulenc product name) Water
────────29.5 parts or more are mixed uniformly to form a flowable agent. [Formulation Example 6] Granular hydrating agent (dry flowable agent) Inventive compound No. 6 ────────75 parts Isoban No. 1 ────────10 copies (
Anionic surfactant: Clary Soprene Chemical Co., Ltd. trade name) Vanilex N ──────── 5 parts (anionic surfactant: Sanyo Kokusaku Pulp Co., Ltd. trade name) Carplex #80──── ──────10 parts or more (white carbon: trade name of Shionogi & Co., Ltd.) are uniformly mixed and pulverized to form a dry flowable agent. [Formulation Example 7] Granule Compound of the Invention No. 6 ────────
Part 1 Bentonite ────────
Part 55 Talc ──────
--- After uniformly mixing and pulverizing 44 parts or more, a small amount of water is added, the mixture is stirred and kneaded, and the mixture is granulated using an extrusion granulator and dried to form granules. When using, the above-mentioned hydrating powders, emulsions, flowable powders, and granular hydrating powders should be diluted 50 to 1000 times with water so that the active ingredient is 0.0 per hectare (ha).
001 to 10 kg. Next, the usefulness of the compounds of the present invention as herbicides will be specifically explained in the following test examples. [Test Example 1] Weeding effect test by soil treatment 15 cm in height,
Fill a plastic box with a width of 22 cm and a depth of 6 cm with sterilized diluvial soil, and then mix and sow velvet, corn, wheat, and soybean. Spread evenly over the surface with a small sprayer. The chemical solution used for spraying was a formulation suitably prepared according to the formulation example described above, diluted with water, and used for spraying. Three weeks after spraying the chemical solution, the herbicidal effect on various plants was investigated according to the following criteria. The results are shown in Table 7. Judgment Criteria 5 - Weed killing rate 90% or more (almost complete death) 4 - Weed killing rate 70-90% 3- Weed killing rate 40-70% 2- Weed killing rate 20-40% 1- Weed killing rate 5-20% 0- Weed killing rate 5% or less (almost no effect) However, the above herbicide rate was determined by the following formula by determining the weight of above-ground plants in the chemically treated area and the weight of above-ground plants in the non-treated area. Weed killing rate = (1 - Weight of above-ground plants in treated area / Weight of above-ground plants in non-treated area) x 100 [Test Example 2] Weeding effect test by foliage treatment 15 cm long, 22 cm wide, 6 cm deep Sterilized diluvial soil was placed in a plastic box, and seeds of dogfish, leafminer, dogwood, corn, wheat, and soybean were sown in spots. 2-3 different plants
When the leaf stage was reached, the active ingredients were uniformly sprayed onto the stems and leaves so that the amount of the active ingredient was at a predetermined ratio. The chemical solution used for spraying was a formulation suitably prepared according to the formulation example described above, diluted with water, and sprayed over the entire surface of the stems and leaves of various plants using a small sprayer. Three weeks after spraying the chemical solution, the herbicidal effect on various plants was investigated according to the criteria of Test Example-1. The results are shown in Table 8. In addition, compound No. in each table. is Compound No. described in Examples. The symbols indicate the following meanings. H (Dogfish), D (Dogberry), I (Doggarashi),
T (corn), W (wheat), S (soybean) [0
124]

Claims (2)

[Claims] Claim 1 General formula (1): [Formula 1] [In the formula, Q represents [Formula 2], and R1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a C 3 to 7 alkyl group. cycloalkyl group, alkyl group having 1 to 6 carbon atoms substituted with cycloalkyl group having 3 to 7 carbon atoms, alkenyl group having 2 to 6 carbon atoms, alkynyl group having 2 to 6 carbon atoms, carbon an alkyl group having 1 to 6 carbon atoms substituted by an alkoxy group having 1 to 6 atoms; an alkyl group having 1 to 6 carbon atoms substituted by a mono- or polyhalogenoalkoxy group having 1 to 6 carbon atoms; an alkyl group having 1 to 6 carbon atoms substituted with an alkylthio group having 1 to 6 carbon atoms; an alkyl group having 1 to 6 carbon atoms substituted by an alkylsulfonyl group having 1 to 6 carbon atoms; , a mono- or polyhalogenoalkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted by a cyano group, a carbon atom substituted by an alkoxycarbonyl group having 1 to 6 carbon atoms An alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with an alkylcarbonyl group having 1 to 6 carbon atoms, a phenyl group, or a benzyl group (however, these phenyl groups and benzyl groups are substituted with halogen one or more substituents selected from atoms, trifluoromethyl groups, nitro groups, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and alkoxycarbonyl groups having 1 to 6 carbon atoms ), and R2 has 1 to 6 carbon atoms.
an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with an alkoxy group having 1 to 6 carbon atoms, a carbon atom An alkyl group having 1 to 6 carbon atoms substituted with an alkylthio group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted by an alkoxycarbonyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms substituted with an alkylthio group having 1 to 6 carbon atoms; 1-6 mono- or polyhalogenoalkyl group, 1-6 carbon atoms
an alkyl group having 1 to 6 carbon atoms substituted with an alkylsulfonyl group, a phenyl group or a benzyl group (
However, these phenyl groups and benzyl groups are selected from halogen atoms, trifluoromethyl groups, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and alkoxycarbonyl groups having 1 to 6 carbon atoms. may be substituted with one or more substituents. ), X represents an oxygen atom or a sulfur atom, and G represents [Chemical formula 3
] A, b, c and d each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or a halogen C1 to C6 alkyl groups mono- or polysubstituted by atoms, C1 to C6 alkoxy groups, C1 to C6 alkyl groups substituted by C1 to C6 alkoxy groups; , an alkoxycarbonyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted by an alkylthio group having 1 to 6 carbon atoms, a carbon substituted by an alkylsulfonyl group having 1 to 6 carbon atoms Alkyl group having 1 to 6 atoms, alkylthio group having 1 to 6 carbon atoms, alkylcarbonyl group having 1 to 6 carbon atoms, cycloalkyl group having 3 to 7 carbon atoms, cycloalkenyl having 3 to 7 carbon atoms group, cyano group, phenyl group or benzyl group (however, these phenyl and benzyl groups are halogen atoms, trifluoromethyl groups, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, carbon may be substituted with one or more substituents selected from an alkoxycarbonyl group having 1 to 6 atoms and a nitro group), a 5- or 6-membered heterocycle (however, these heterocycles may be substituted with a nitrogen atom , contains 1 to 3 heteroatoms selected from oxygen atoms and sulfur atoms in the ring.Also, contains a sulfonyl group.In addition, these heterocycles include an alkyl group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms,
6 alkoxy group, a halogen atom, a trifluoromethyl group, a nitro group, and an alkoxycarbonyl group having 1 to 6 carbon atoms. ), naphthyl group, benzene-fused heterocycle (however, these benzene-fused heterocycles contain 1 to 2 heteroatoms selected from nitrogen atoms, oxygen atoms, and sulfur atoms in the ring. , alkyl group having 1 to 6 carbon atoms, 1 carbon atom
It may be substituted with one or more substituents selected from -6 alkoxy groups, halogen atoms, trifluoromethyl groups, nitro groups, and alkoxycarbonyl groups having 1 to 6 carbon atoms. ) represents. ] Substituted aminosulfonamide derivatives and agriculturally suitable salts thereof. 2. A selective herbicide comprising the compound according to claim 1 as an active ingredient.