JPH04253974A - Sulfonylurea compound, its production and herbicide containing the same - Google Patents

Abstract

PURPOSE:To provide a new compound useful as an active component of a herbicide exhibiting broad herbicidal spectrum at low rate of application. CONSTITUTION:The compound of formula I (R<1> is cycloalkyl, alkoxyalkyl, phenyl, pyridyl, thienyl, furyl, pyrazolyl or pyrazinyl; R<2> is alkyl, haloalkyl, etc.; R<3> is H, halogen, alkyl, etc.; X and Y are halogen, alkyl, alkoxy, etc.; A is =CH- or =N-), e.g. 4-trifluoromethyl-N-[6-[[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl]aminosulfonyl]pyridin-2-yl]-N-methylbenzamide. The compound can be produced by reacting a compound of formula II [Z<1> is -NH2, -NCO or -NHCO2R<4> (R<4> is alkyl or aryl)] with a compound of formula III (Z<2> is -NH2 when Z<1> is -NCO or -NHCO2R<4> and Z<2> is -NCO or -NHCO2R<4> when Z<1> is -NH2).

Description

[Detailed description of the invention]

0001

TECHNICAL FIELD The present invention relates to novel sulfonylurea compounds or salts thereof, methods for producing them, and herbicides containing them.

0002

[Prior Art] U.S. Pat. No. 4,946,494 describes pyridine sulfonylurea derivatives useful as active ingredients of herbicides. The structure differs in the substituent at the 6-position of the ring.

0003

[Structure of the Invention] The present invention relates to sulfonylurea compounds represented by the general formula (I) below or salts thereof, methods for producing them, herbicides containing them, and intermediates for producing the compounds. Regarding. General formula (I)

embedded image (wherein R1 is a cycloalkyl group, an alkoxyalkyl group, an optionally substituted phenyl group, an optionally substituted pyridyl group, an optionally substituted thienyl group, an optionally substituted furyl group, an optionally substituted pyrazolyl group or an optionally substituted pyrazinyl group, R2 is an alkyl group,
A haloalkyl group, a cycloalkyl group, a phenyl group, or a benzyl group, R3 is a hydrogen atom, a halogen atom, an alkyl group, or a haloalkyl group, and X and Y are each independently a halogen atom, an alkyl group, an alkoxy group, or a haloalkoxy and A is =CH- or =N-)

In the general formula (I), an optionally substituted phenyl group, an optionally substituted pyridyl group, an optionally substituted thienyl group, an optionally substituted furyl group, an optionally substituted furyl group, and an optionally substituted furyl group included in R1 Good examples of substituents for the pyrazolyl group and the optionally substituted pyrazinyl group include halogen atoms,
Alkyl group, haloalkyl group, alkoxy group, -NO2
group, -CN group, -CO2R5 group, -SO2CH3 group, etc., and R5 is a hydrogen atom or an alkyl group. Moreover, the number of substitutions of these substituents may be 1 or 2 or more, and when the number of substitutions is 2 or more, the types of substituents may be the same or different.

In general formula (I), R1, R2, R3, R5
, X and Y include those having 1 to 6 carbon atoms, such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, etc. The cycloalkyl group included in R1 and R2 includes those with structural isomerism of branched aliphatic chains, such as those having 3 to 6 carbon atoms, such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc. . Also, R1, R2, R3, X
The halogen atoms contained in Y include fluorine, chlorine,
Examples include bromine or iodine atoms.

Examples of the salt of the sulfonylurea compound represented by the general formula (I) include salts of alkali metals such as sodium and potassium, salts of alkaline earth metals such as magnesium and calcium, and amines such as monomethylamine, dimethylamine and trimethylamine. Salt is an example.

The sulfonylurea compound represented by the general formula (I) can be produced, for example, by the following methods [A] to [D].

[A]

[C5] [B]

[C6] [C]

[C7] [D]

[Chemical formula 8]

During the reactions [A] to [D], R1, R2, R
3, X, Y and A are as described above, and R4 is an alkyl group or an aryl group.

As the alkyl group represented by R4, R
1, R2, R3, R5, the same alkyl groups as those mentioned above for Examples include groups.

Reaction [A] is carried out in the presence of a base, and reactions [B], [C] and [D] are also carried out in the presence of a base, if necessary. As a base, tertiary amine such as triethylamine, 1,8-diazabicyclo[5.4.0
]-7-undecene etc. are used.

[0012] Also, reactions [A], [B], [C] and [D
] is usually carried out in the presence of a solvent. As a solvent,
Aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; Cyclic or acyclic aliphatic hydrocarbons such as chloroform, carbon tetrachloride, methylene chloride, dichloroethane, trichloroethane, hexane, and cyclohexane; diethyl ether, dioxane, tetrahydrofuran, etc. Nitriles such as acetonitrile, propionitrile, and acrylonitrile; Ketones such as acetone and methyl ethyl ketone; esters such as methyl acetate and ethyl acetate; and aprotic polar solvents such as dimethyl sulfoxide and sulfolane.

[0013] The reaction temperature of reaction [A] is usually -20 to +1
00°C, preferably 0 to 40°C, and the reaction time is 0.00°C, preferably 0 to 40°C.
01 to 100 hours, preferably 0.1 to 24 hours, the reaction temperature of reaction [B] is usually 0 to 150 °C, the reaction time is 0.1 to 24 hours, and the reaction time of reaction [C] is usually 0 to 150 °C. The temperature is usually 0-150°C, and the reaction time is 0.1-24°C.
time, and the reaction temperature of reaction [D] is usually -20 to +1
The temperature is 50°C and the reaction time is 0.1 to 24 hours.

The sulfonylurea compound represented by the general formula (I) can also be produced, for example, by the following method [E].

[E]

[Chemical formula 9]

(wherein R1, R2, R3, X, Y and A
is as described above)

Reaction [E] is usually carried out in the presence of a base and a solvent, which may be the same as those used in reactions [A] to [D] above.

[0018] The reaction temperature of reaction [E] is usually -10 to +1
The temperature is 50°C, preferably room temperature to 100°C, and the reaction time is 0.1 to 48 hours, preferably 0.5 to 24 hours.

The substituted pyridine compound represented by (II-1) in reactions [A] and [B] is a new compound, and can be produced, for example, by the following methods [F] and [G]. Can be done.

[F]

[Chemical formula 10]

In reaction [F], each of reaction steps 1 to 17 has the following reaction conditions. 1. PhCH2SH, base, solvent, 80-170°C2.
(i) 50% aq. Acetic acid, Cl2, -10 to +10°C (ii) Bu(t)-NH2, solvent, 0°C to room temperature3. R
2NH2, optionally CuCl and/or solvent, 10
0-200℃ 4. R1COCl, solvent, base, -10 to +100°C5
．． CF3CO2H, room temperature to reflux temperature6. NH3, optionally CuCl and/or solvent, 1
00-200℃ 7. R2T', base, solvent, -10 to +100°C8. (
i) 50% aq. Acetic acid, Cl2, -10 to +10°C (ii) Bu(t)-NH2, solvent, 0°C to room temperature9. R
1 COCl, solvent, base, -10 to +100°C10. (
i) 50% aq. Acetic acid, Cl2, -10 to +10°C (ii) Bu(t)-NH2, solvent, 0°C to room temperature 11.
(i) 50% aq. Acetic acid, Cl2, -10 to +10°C (ii) NH3, solvent, 0°C to room temperature 12. R1COCl, solvent, base, -10 to +100°C
13. R2T', solvent, base, -10 to +100℃14
．． NH3, solvent, CuCl as necessary, 100-20
0℃ 15. R1COCl, solvent, base, -10°C to room temperature 16
．． R2T', solvent, base, -10 to +100°C17. R
2T', solvent, base, -10 to +100°C

[0022]
[G]

[Chemical formula 11]

In reaction [G], each of reaction steps 18 to 26 has the following reaction conditions. 18. NH3, solvent, CuCl as necessary, 100~
200℃ 19. R1COCl, base, solvent, -10 to +100°C
20. R2T', base, solvent, -10 to +100℃21
．． NaSH, solvent, 50-200°C or (i) SC(N
H2) 2, acetic acid, solvent if necessary, 50°C to reflux temperature (ii) base, solvent if necessary, 0 to 100°C22.
(i) 50% aq. Acetic acid, Cl2, -10 to +10°C (ii) NH3, solvent, 0°C to room temperature 23. R2NH2, solvent, CuCl if necessary, 10
0-200℃ 24. R1COCl, base, solvent, -10 to +100°C
25. PhCH2SH, base, solvent, 80-170℃2
6. (i) 50% aq. Acetic acid, Cl2, -10 to +10
°C (ii) NH3, solvent, 0 °C to room temperature

In reactions [F] and [G], R1, R2 and R3 are as described above, and T and T' are each independently a halogen atom such as chlorine or bromine. In addition, Ph represents a phenyl group, Bu(t) represents a tertiary butyl group, and aq.
indicates an aqueous solution.

The compound represented by (II-2) in reaction [C] can be prepared, for example, by the following method [H], and the compound represented by (II-3) in reaction [D] can be prepared by the following method [H]. ,
For example, it can be manufactured by the following method [I].

In reaction formula [H] or [I], R1, R2, R3 and R4
is as described above.

The compound represented by (IV) in the above reaction formula [E] can be produced using the compound represented by (VI) in the above reaction [F], for example, by the following method [J]. can do.

[J]

[Chemical formula 12]

(wherein R2, R3, X, Y, A and Ph
is as described above)

Reaction [J] The reaction temperature in the first step is usually room temperature to reflux temperature, the reaction time is 0.1 to 24 hours, preferably 0.5 to 5 hours, and the reaction temperature in the second step is usually 0.1 to 24 hours, preferably 0.5 to 5 hours. ℃
- reflux temperature, preferably 10°C - room temperature, and reaction time is 0.05-24 hours, preferably 0.1-1 hour.

[0031] Furthermore, R1COC in reactions [E] to [G]
The compound represented by l can be produced, for example, by the following method [K]. Solvent, catalyst if necessary, 50°C to reflux temperature (in the formula, R1 is as described above)

The compound represented by R1CO2H in reaction [K] can be easily obtained by a conventional method, but in the case of optionally substituted picolinic acid, it can be produced, for example, by the following method [L]. Good too.

[L]

[Chemical formula 13]

{In the formula, T is as described above, R6 is a halogen atom, alkyl group, haloalkyl group, alkoxy group, -NO2 group, and n is an integer of 0 to 4 (n is 2 to 4
R6 may be the same or different when R6 is an integer)

[0035] The reaction conditions for each reaction [F] to [L], such as reaction temperature, reaction time, solvent (solvent used as necessary), basic substance, and catalyst used as necessary, are particularly Unless otherwise specified, the reaction conditions can be selected appropriately from the reaction conditions of similar reactions.

Further, the salt of the sulfonylurea compound represented by the general formula (I) can be easily obtained by a conventional manufacturing method.

As shown in the test examples below, the sulfonylurea compound represented by the general formula (I) exhibits a wide herbicidal spectrum at low doses, and at the same time shows safety against wheat, soybean, or sugar beet. include. Therefore, the general formula (I
) or a salt thereof is useful as an active ingredient of herbicides.

When applying the herbicide of the present invention containing the compound represented by formula (I) or a salt thereof as an active ingredient, a carrier, if necessary a diluent, a solvent, an emulsifier,
It is used by mixing with various auxiliary agents such as spreading agents and surfactants to formulate granules, wettable powders, wettable powders, emulsions, solutions, suspensions, etc. A suitable weight ratio of the active ingredient compound to the pesticide adjuvant is generally 1:99 to 90:10, preferably 5:95 to 80:20. The appropriate amount of the active ingredient compound to be used cannot be determined unconditionally due to differences in weather conditions, soil conditions, drug formulation, target weed type, application period, etc., but in general, the amount of the active ingredient applied per are is 0.
．． 005g to 50g, preferably 0.01g to 10g,
More preferably, it is 0.05g to 5g.

Examples of formulations of the herbicide of the present invention are described below. Put each of the above ingredients into a high-speed mixing granulator, and then add 2
Add 0% water, granulate and dry to obtain a granular wettable powder.

Formulation Example 2 (Product name: Shionogi & Co., Ltd.) (1) to (4) above
A mixture of components and compound NO. 48 in a weight ratio of 9:1 to obtain a wettable powder.

Formulation example 3 A hydrating agent can be obtained by mixing the above components.

Formulation example 4 A hydrating agent can be obtained by mixing the above components.

Formulation Example 5 The above components (1) to (4) are mixed uniformly and pulverized with a Dyno Mill (manufactured by Willy & Verhohen) to obtain a suspension composition.

Formulation Example 6 The above components are uniformly mixed and wet-pulverized to obtain an aqueous suspension.

The herbicide of the present invention can be mixed or used in combination with other agricultural chemicals, agricultural chemical auxiliaries, phytotoxicity reducers, etc., and in this case may exhibit even better effects and action. When mixed or used in combination with other herbicides, examples of the active ingredients of the herbicides to be mixed include the following.・
(±)-2-[4-[(6-chloro-2-quinoxalinyl)oxy]phenoxy]ethylpropionate (common name: quizalofopethyl)・3-(1-methylethyl)-
(1H)-2,1,3-benzothiadiazine-4-(3
H)-one-2,2-dioxide (common name; bentazone)/sodium 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate (common name;
acifluorfen)・2-[[[[(4-chloro-6
-methoxy-2-pyrimidinyl)amino]carbonyl]
Amino]sulfonyl]ethyl benzoate (common name; Chloimuron-ethyl)
(±)-5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid 2-ethoxy-1
-Methyl-2-oxoethyl (common name: lactofen)
・4-(2,4-dichlorophenoxy)butyric acid (common name;
2,4-DB:2,4-DB)・2-chloro-N
-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide (common name: metolachlor) (±)-2-[4-[(6-chloro-
Ethyl 2-benzoxazolyloxy[phenoxy]propionate (common name: fenoxaprop ethyl) (
±)-2-[4-[[5-(trifluoromethyl)-2
-pyridinyl]oxy]phenoxy]butyl propionate (common name: fluazifop)・2-chloro-N-(2
,6-diethylphenyl)-N-(methoxymethyl)acetamide (common name: alachlor)・3-(3,4-
dichlorophenyl)-1-methoxy-1-methylurea (
Generic name: linuron)・4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazin-5-(4H)-one (generic name: metribuzin)・2 -[1-(ethoxyimino)butyl]-5-[2
-(ethylthio)propyl]-3-hydroxy-2-cyclohexen-1-one (common name: setoxydim) (
±)-2-[4,5-dihydro-4-methyl-4-(1
-methylethyl)-5-oxo-1H-imidazole-
2-yl]-5-ethyl-3-pyridinecarboxylic acid (generic name: imazethapyr) 5-[2-chloro-4-(trifluoromethyl)phenoxy]-N-(methylsulfonyl)-2-nitrobenzamide ( Generic name: Fomesafen)・2-[4,5-dihydro-4-methyl-4-(1-
methylethyl)-5-oxo-1H-imidazole-2
-yl]-3-quinolinecarboxylic acid (generic name: imazaquin)・2,6-dinitro-N,N-dipropyl-4-(
trifluoromethyl)aniline (common name; trifluralin), 3-[(methoxycarbonyl)amino]phenyl (3-methylphenyl)carbamate (common name; phenmedipham), ethyl [3-[[(phenylamino)carbonyl] Oxy]phenyl]carbamate (generic name: desmedipham), 7-oxabicyclo[
2.2.1] Heptane-2,3-dicarboxylic acid (generic name; Endothal)・Ethyl diisopropylthiocarbamate (generic name; EPTC)・
Methyl 2-[4-[(3-chloro-5-(trifluoromethyl)-2-pyridinyl]oxy]phenoxy]propionate (common name: haloxyfop), (±)-2-ethoxy-2-methanesulfonic acid, 3-dihydro-3,3-
Dimethyl-5-benzofuranyl (common name: ethofumesate), 5-amino-4-chloro-2-phenyl-3-(
2H)-pyridazinone (generic name: chloridazone)・2-
[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]methyl benzoate (common name; metsulfuron-methyl) 6-(4- Methyl isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-m-toluate and 2-(4-isopropyl-4-methyl-5-
Methyl oxo-2-imidazolin-2-yl)-P-toluate (generic name: imazametabenz)・1,2-dimethyl-3,5-diphenyl-1H-pyrazoline methyl sulfate (generic name: dipenzocort)・3, 6-dichloro-2-methoxybenzoic acid (common name: dicamba) 3
, 5-dibromo-4-hydroxybenzonitrile (common name: bromoxynil), 4-hydroxy-3,5-diiodobenzonitrile (common name: ioxynil), 2,
4-dichlorophenoxyacetic acid (common name: 2,4-di-
:2,4-D)N'-(3,4-dichlorophenyl)-
N,N-dimethylurea (common name: diuron)・2-[[
[[N-(4-Methoxy-6-methyl-1,3,5-triazin-2-yl)methylamino]carbonyl]amino]sulfonyl]methylbenzoate (common name; tribenuron) s-(2 ,3,3-trichloro-2-propenyl)-bis-(1-methylethyl) thiocarbamate (common name: trialate).
2-chloro-N-[[(4-methoxy-6-methyl-1
,3,5-triazin-2-yl]amino]carbonyl]benzenesulfonamide (common name: chlorsulfuron)・3-[[[[(4-methoxy-6-methyl-1,3
,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]-2-thiophenecarboxylic acid methyl (common name; thiameturon-methyl: thiametur
on-methyl)・(±)-2-[4-(2,4-
Dichlorophenoxy) phenoxy]methyl propionate (common name: diclofop-methyl), 4-chloro-2-
Methylphenoxyacetic acid (generic name; MCP: M
CPA)・4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazine-5
-(4H)-one (generic name: metribuzin)・3,6-
Dichloro-2-pyridinecarboxylic acid (common name: clopyralid), 4-amino-3,5,6-trichloro-2-pyridinecarboxylic acid (common name: picloram), O-(6-
Chloro-3-phenyl-4-pyridazinyl)-S-octyl thiocarbamate

The scope of application of the herbicide of the present invention is wide-ranging, including agricultural land such as fields, orchards, and mulberry orchards, as well as non-agricultural land such as mountains and forests, farm roads, grounds, and factory sites. Application methods include soil treatment, foliage treatment, etc. You can choose as appropriate.

[0047]

EXAMPLES Specific synthesis examples and biological test examples of the compounds of the present invention are described below, but the present invention is not limited thereto.

Synthesis Example 1 4-Trifluoromethyl-N-[6-[[(4,6-dimethoxypyrimidine-2
Synthesis of -yl)aminocarbonyl]aminosulfonyl]pyridin-2-yl]-N-methylbenzamide (compound No. 48 below)

1) 2,6-dichloropyridine 250
A mixture of 500 ml of dimethyl sulfoxide and 256.8 g of anhydrous potassium carbonate was heated to 110°C. 230.4 g of benzyl mercaptan was dropped into this over about 1 hour. After the dropwise addition was completed, the reaction was continued at 110° C. for about 1 hour. After the reaction was completed, the reaction mixture was poured into 1000 ml of water and extracted with methylene chloride. 1 layer of methylene chloride
After washing with 0% aqueous sodium hydroxide solution, it was washed with water and dried over anhydrous sodium sulfate. Thereafter, by distilling off methylene chloride under reduced pressure, an oily 2-benzylthio-
430 g of 6-chloropyridine was obtained.

2) A mixed solution of 430 g of 2-benzylthio-6-chloropyridine, 500 ml of acetic acid and 900 ml of water was cooled with ice, and chlorine gas was introduced at 0°C to 5°C. The mixture was introduced and reacted until excess chlorine gas was detected. After the reaction was completed, nitrogen gas was bubbled into the reaction system to drive out excess chlorine gas. The reaction product was poured into ice water, extracted with methylene chloride, and the methylene chloride layer was washed with ice water and then dried over anhydrous sodium sulfate. Next, the methylene chloride solution was ice-cooled, and 401 g of tert-butylamine was added dropwise over about 2 hours to cause a reaction. After the reaction was completed, it was poured into water and the liquid was separated. Dry the methylene chloride layer with anhydrous sodium sulfate,
Methylene chloride was distilled off. A mixture of ether and n-hexane was added to the residue for crystallization, and the resulting crystals were collected by filtration and dried under reduced pressure to obtain 280 g of 6-chloro-N-tert-butyl-2-pyridinesulfonamide.

3) 25 g of 6-chloro-N-tert-butyl-2-pyridine sulfonamide, 150 ml of 20% methylamine aqueous solution and 0.5 g of cuprous chloride
Pour into a 00ml mini autoclave and heat at 150℃ for approx.
Allowed time to react. After the reaction was completed, the mixture was allowed to cool and the contents were poured into water. The resulting crystals were collected by filtration, washed with water, and dried to obtain 22.7 g of the desired product having a melting point of 157 to 160°C.

4) Dissolve 1.0 g of N-tert-butyl-6-methylamino-2-pyridinesulfonamide and 0.42 g of triethylamine in 20 ml of 1,2-dichloroethane, and add to the solution while stirring at room temperature.
-Trifluoromethylbenzoyl chloride 0.86g
was added thereto, and the reaction was then carried out under stirring at reflux temperature for 20 hours. After the reaction, the solvent was distilled off under reduced pressure and purified by silica gel column chromatography to obtain N-
1.3 g of [6-(tert-butylaminosulfonyl)pyridin-2-yl]-4-trifluoromethyl-N-methylbenzamide was obtained.

5) Add 20 ml of trifluoroacetic acid to 2.0 g of N-[6-(tert-butylaminosulfonyl)pyridin-2-yl]-4-trifluoromethyl-N-methylbenzamide, and stir at room temperature for 20 hours. I reacted below. After the reaction, the solvent was distilled off under reduced pressure and purified by silica gel column chromatography to obtain a melting point of 160-1.
N-[6-(aminosulfonyl)pyridine-2 at 62°C
1.33 g of -yl]-4-trifluoro-N-methylbenzamide was obtained.

6) N-[6-(aminosulfonyl)
pyridin-2-yl]-4-trifluoro-N-methylbenzamide 1.0 g and phenyl (2,4-dimethoxypyrimidin-2-yl)carbamate 0.76 g
was dissolved in 20 ml of acetonitrile, and while stirring at room temperature, 1,8-diazahicyclo[5.4.0]
Add 0.42 g of -7-undecene, then 20 g at room temperature.
The reaction was allowed to take place under stirring for an hour. After the reaction was completed, water was added to the reaction solution, acidified with hydrochloric acid, and extracted with 200 ml of ethyl acetate. Thereafter, it was dried over Glauber's salt, and the solvent was distilled off under reduced pressure. The obtained residue was crystallized using an ether-hexane solution, and the precipitated crystals were collected by filtration and dried under reduced pressure to give a melting point of 139~139.
1.0 g of the target product was obtained at 141°C.

Synthesis Example 2 6-Bromo-N-[6-
[[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]aminosulfonyl]pyridin-2-yl]-N-methylpicolinic acid amide (compound No. 5 below)
8) Synthesis

1) 11 g of 2,6-dibromopyridine
A mixture of 60 ml of N,N-dimethylformamide and 4.37 g of copper cyanide was reacted under reflux for about 2 hours. After the reaction was completed, the mixture was allowed to cool, poured into 200 ml of 28% aqueous ammonia, and extracted with methylene chloride. After drying the methylene chloride layer over anhydrous sodium sulfate, the methylene chloride was distilled off, and the residue was purified by silica gel column chromatography to obtain 1.6 g of 2-bromo-6-cyanopyridine with a melting point of 101-104°C. .

2) 1.4 g of 2-bromo-6-cyanopyridine, 0.46 g of sodium hydroxide and 15 ml of water
The mixture was reacted under reflux for about 1 hour. After the reaction was completed, it was allowed to cool and was poured into water. After washing with 50 ml of methylene chloride, the aqueous layer was adjusted to pH 2 with concentrated hydrochloric acid to precipitate crystals. The resulting crystals were collected by filtration and dried under reduced pressure to obtain 1.17 g of 6-bromopicolinic acid.

3) 6-bromopicolinic acid 1.16g
A mixed solution of 15 ml of phosphorus oxychloride was reacted under reflux for about 3 hours. After the reaction was completed, excess phosphorus oxychloride was distilled off under reduced pressure, and 25 ml of 1,2-dichloroethane was added to the residue, followed by 1.3 g of N-tert-butyl-6-methylaminopyridin-2-ylsulfonamide. Ta. 0.81 g of triethylamine was added dropwise into this at room temperature over about 15 minutes. After the dropwise addition was completed, the reaction was allowed to proceed at room temperature for about 1 hour. After the reaction was completed, the reaction solution was poured into water and extracted with methylene chloride. After drying the methylene chloride layer over anhydrous sodium sulfate, the methylene chloride was distilled off. The residue was purified by silica gel column chromatography to give a melting point of 174-1.
2.01 g of 6-bromo-N-(6-tert-butylaminosulfonylpyridin-2-yl)-N-methylpicolinamide at 76°C was obtained.

4) 6-bromo-N-(6-tert-butylaminosulfonylpyridin-2-yl)-N
- a mixture of 1.6 g methylpicolinic acid amide and 20 ml trifluoroacetic acid at room temperature for 3 hours, then at 40°C for 1 hour.
Allowed time to react. After the reaction was completed, excess trifluoroacetic acid was distilled off, and ether was added to the residue for crystallization. The resulting crystals were collected by filtration and dried under reduced pressure to give N-(6-aminosulfonylpyridin-2-yl)-6 with a melting point of 178-182°C.
1.24 g of -bromo-N-methylpicolinic acid amide was obtained.

5) 0.25 g of N-(6-aminosulfonylpyridin-2-yl)-6-bromo-N-methylpicolinic acid amide, 0.19 g of phenyl(2,4-dimethoxypyrimidin-2-yl)carbamate After adding 0.1 g of 1,8-diazabicyclo[5.4.0]-7-undecene to a mixture of 1,8-diazabicyclo[5.4.0]-7-undecene and 5 ml of acetonitrile at room temperature, the mixture was reacted at room temperature for 10 minutes. After the reaction was completed, the reaction mixture was poured into water, made weakly acidic with hydrochloric acid, and the precipitated solid was collected by filtration, washed with water, and dried to obtain 0.34 g of the desired product having a melting point of 180 to 185°C.

[0061] General formula (I) produced according to the above synthesis example
Representative examples of compounds represented by I-1) are listed in Table 1.

[0062]

[Table 1]

[0063]

[Table 2]

[0064]

[Table 3]

[0065]

[Table 4]

[0066]

[Table 5]

[0067]

[Table 6]

Next, Table 2 lists representative examples of compounds represented by the general formula (I) produced according to the above synthesis example.

[0069]

[Table 7]

[0070]

[Table 8]

[0071]

[Table 9]

[0072]

[Table 10]

[0073]

[Table 11]

[0074]

[Table 12]

[0075]

[Table 13]

[0076]

[Table 14]

[0077]

[Table 15]

Test Example 11/1,500 are pots were filled with field soil and seeds of various plants were sown. After that, the plants grow at a certain leaf age (rice 1.3-3.7 leaf stage, soybean primary leaf stage - 1.5 leaf stage, maize 2.0-4.3 leaf stage, cotton cotyledon stage - 1.2 leaf stage, Wheat 2.0-2.8 leaf stage, Japanese fir 1.7-3.5 leaf stage, morning glory 0.2-2.5 leaf stage, golden deer 0.1-2.5 leaf stage, blueberry 0
．． 1 to 2.5 leaf stage, barnyard grass 1.5 to 4.0 leaf stage, crabgrass 1.2 to 2.0 leaf stage), apply a predetermined amount of the hydrating agent of the herbicide of the present invention. Weighed and diluted in 5 liters of water per are. Furthermore, 0.0% of an agricultural spreading agent was added to the aqueous solution.
2% and treated the leaves with a small spray. 18 to 35 days after treatment, the growth status of various plants was visually observed and surveyed, and the results were graded into 10 grades (1: same as untreated area).
The degree of growth inhibition was evaluated at 10: complete inhibition), and the results shown in Table 3 were obtained.

[0079]

[Table 16]

[0080]

[Table 17]

[0081]

[Table 18]

[0082]

[Table 19]

[0083]

[Table 20]

[0084]

[Table 21]

[0085]

[Table 22]

Test Example 2 A 1/10,000 are pot was filled with field soil, and wheat and wild oat seeds were sown in separate pots. After that, wheat is 1.8-2
．． When the wild oats reached the 5-leaf stage and the 1.1-1.5 leaf stage, a predetermined amount of the wetting agent of the herbicide of the present invention was weighed out and diluted with 5 liters of water per are. Further, an agricultural spreading agent was added to the aqueous solution at a concentration of 0.2%, and the foliage was treated with a small sprayer. 20 to 23 days after the treatment, the growth status of each plant was visually observed and the degree of growth inhibition was evaluated using the same method as in Test Example 1, and the results shown in Table 4 were obtained.

[0087]

[Table 23]

Test Example 3 Upland soil was filled in a 1/10,000 are pot, and sugar beet (sugar beet) seeds were sown. Thereafter, when the sugar beet reached the two-leaf stage, a predetermined amount of the hydrating agent of the herbicide of the present invention was weighed out and diluted with 5 liters of water per area. Further, an agricultural spreading agent was added to the aqueous solution at a concentration of 0.2%, and the foliage was treated with a small sprayer. On the 18th day after the treatment, the growth conditions of the various plants were observed and investigated with the naked eye, and the degree of growth inhibition was evaluated using the same method as in Test Example 1, and the results shown in Table 5 were obtained.

[0089]

[Table 24]

Claims (4)

[Claims] Claim 1: General formula (I) [Formula 1] (wherein R1 is a cycloalkyl group, an alkoxyalkyl group, an optionally substituted phenyl group, an optionally substituted pyridyl group, an optionally substituted thienyl group) group, an optionally substituted furyl group, an optionally substituted pyrazolyl group, or an optionally substituted pyrazinyl group, and R2 is an alkyl group,
A haloalkyl group, a cycloalkyl group, a phenyl group, or a benzyl group, R3 is a hydrogen atom, a halogen atom, an alkyl group, or a haloalkyl group, and X and Y are each independently a halogen atom, an alkyl group, an alkoxy group, or a haloalkoxy and A is =CH- or =N-)
A sulfonylurea compound or a salt thereof. [Claim 2] General formula (II) [Formula 2] (wherein, R1 is a cycloalkyl group, an alkoxyalkyl group, an optionally substituted phenyl group, an optionally substituted pyridyl group, an optionally substituted thienyl group) group, an optionally substituted furyl group, an optionally substituted pyrazolyl group, or an optionally substituted pyrazinyl group, and R2 is an alkyl group,
is a haloalkyl group, cycloalkyl group, phenyl group or benzyl group, R3 is a hydrogen atom, halogen atom, alkyl group or haloalkyl group, Z1 is -NH2 group,
-NCO group or -NHCO2R4 group, R4 is an alkyl group or aryl group), and a substituted pyridine compound represented by the general formula (III) [Formula 3] (wherein, X and Y are each independently It is a halogen atom, an alkyl group, an alkoxy group or a haloalkoxy group, A is =CH- or =N-, Z2 is a -NH2 group when Z1 is -NCO group or -NHCO2R4 group, and Z1 is -NH2 In the case of the group, it is a -NCO group or -NHCO2R4 group, and R4 is as described above).
I) A method for producing a sulfonylurea compound represented by the following formula (wherein R1, R2, R3, X, Y and A are as described above) or a salt thereof. 3. General formula (I) [Formula 1] (wherein, R1 is a cycloalkyl group, an alkoxyalkyl group, an optionally substituted phenyl group, an optionally substituted pyridyl group, an optionally substituted thienyl group) group, an optionally substituted furyl group, an optionally substituted pyrazolyl group, or an optionally substituted pyrazinyl group, and R2 is an alkyl group,
A haloalkyl group, a cycloalkyl group, a phenyl group, or a benzyl group, R3 is a hydrogen atom, a halogen atom, an alkyl group, or a haloalkyl group, and X and Y are each independently a halogen atom, an alkyl group, an alkoxy group, or a haloalkoxy and A is =CH- or =N-)
A herbicide characterized by containing a sulfonylurea compound represented by the following or a salt thereof as an active ingredient. [Claim 4] General formula (II-1) [Formula 4] (wherein, R1 is a cycloalkyl group, an alkoxyalkyl group, an optionally substituted phenyl group, an optionally substituted pyridyl group, an optionally substituted pyridyl group, or an optionally substituted pyridyl group) a thienyl group, an optionally substituted furyl group, an optionally substituted pyrazolyl group, or an optionally substituted pyrazinyl group, R2 is an alkyl group,
A substituted pyridine compound represented by a haloalkyl group, a cycloalkyl group, a phenyl group, or a benzyl group, and R3 is a hydrogen atom, a halogen atom, an alkyl group, or a haloalkyl group.