JPH04257580A - Sulfonamide-based compound, its production and herbicide containing the same compound - Google Patents

Abstract

PURPOSE:To obtain a new compound useful as an agricultural and horticultural herbicide showing a wide herbicidal spectrum with a small amount of herbicide. CONSTITUTION:A compound shown by formula I (R<1> is haloalkyl, alkenyl or haloalkoxy; R<2> is H, alkyl, haloalkyl, cycloalkyl, phenyl or benzyl; R<3> is H, halogen, alkyl or haloalkyl; X and Y are halogen, alkyl, alkoxy or haloalkoxy; A is =CH- or =N-) such as 5-chloro-N-[6-[[[[(4.6-dimethoxypyrimidin-2yl) amino]carbonyl]amino]sulfonyl]pyridine-2yl]-1N-methylvaleramide. The compound is obtained by reacting a compound shown by formula II [Z<1> is NH2, NCO, NHCO2R<4> (R<4> is alkyl or aryl)] with a compound shown by 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

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to novel sulfonamide compounds that are effective as herbicides for agriculture and horticulture.

0002

[Prior Art] U.S. Pat. No. 4,946,494 describes pyridine sulfonylurea derivatives useful as active ingredients of herbicides. are different.

0003

[Structure of the Invention] The present invention relates to sulfonamide 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)

[Chemical 1
] (In the formula, R1 is a haloalkyl group, alkenyl group, or haloalkoxy group, R2 is a hydrogen atom, an alkyl group, 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, X and Y are each independently a halogen atom, an alkyl group, an alkoxy group, or a haloalkoxy group, and A is =CH- or =N-).

In the general formula (I), the alkyl group and alkyl moiety contained in R1, R2, R3, X and Y have 1 to 6 carbon atoms, such as methyl group, ethyl group, propyl group, butyl group, Examples include pentyl group, hexyl group, etc., and the alkenyl group contained in R1 has 2 to 2 carbon atoms.
6, such as vinyl group, allyl group, propenyl group,
Examples thereof include butenyl group, pentenyl group, hexenyl group, etc., and they also include structural isomers of straight chain or aliphatic chain. Furthermore, the cycloalkyl group contained in R2 is
Examples include those having 3 to 6 carbon atoms, such as cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group. Further, the halogen atoms contained in R1, R2, R3, good.

Examples of the salts of the sulfonamide compound represented by the general formula (I) include alkali metal salts such as sodium and potassium salts, alkaline earth metal salts such as magnesium and calcium, and amine salts such as monomethylamine, dinutylamine, and trimethylamine. can be mentioned.

The sulfonamide 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]

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

[Chemical formula 9]

Furthermore, among the compounds represented by the general formula (I), some of the compounds in which R1 is an alkenyl group can also be produced, for example, by the following method [F]. [F]

[Chemical formula 10]

[0010] During the reaction of [A] to [F], R1, R2, R
3. is a halogen atom.

[0011] The alkyl group and halogen atom contained in R4 and R5 include those mentioned above for R1, R2, R3, X and Y, and the aryl group contained in R4 includes a phenyl group, chlorine Examples include a phenyl group substituted with an atom, a phenyl group substituted with a methyl group, and a naphthyl group.

Reactions [A], [E] and [F] are usually 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 the base, tertiary amine such as triethylamine, 1,8-diazabicyclo[5.4.0]-7-undecene, etc. are used.

[0013] Reactions [A] to [F] are 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; Ethers such as diethyl ether, dioxane, and tetrahydrofuran; Nitriles such as acetonitrile, propionitrile, and acrylonitrile Ketones such as acetone and methyl ethyl ketone; Esters such as methyl acetate and ethyl acetate; Aprotic polar solvents such as dimethyl sulfoxide and sulfolane.

[0014] 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
50°C, the reaction time is 0.1 to 24 hours, and the reaction temperature for reaction [E] is usually -10 to +150°C, preferably room temperature to 100°C, and the reaction time is 0.1 to 48 hours. , desirably 0.5 to 24 hours, the reaction temperature of reaction [F] is usually -10 to +150°C, and the reaction time is 0.5 to 24 hours. In addition, in the reaction [F], the general formula (
The compound represented by I-2) can be used in the above reactions [A] to [D
] can be synthesized according to the method.

The substituted pyridine compound represented by (II-1) in reactions [A] and [B] can be used, for example, in the following [G]
and [H].

[G]

[Chemical formula 11]

In reaction [G], 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

[0018]
[H]

[Chemical formula 12]

In reaction [H], 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, -10~1100℃
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 [G] and [H], 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.

Further, the compound represented by (II-2) in reaction [C] can be prepared, for example, by the following method [I], and the compound represented by (II-3) in reaction [D] can be prepared by, for example, the following method [I]. ,
For example, it can be manufactured by the following method [J]. In reaction formula [I] or [J], (II-1), (I
In the compounds represented by I-2) and (II-3), R1
, R2, R3 and R4 are 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 [G], for example, by the following method [K]. can do. [K]

embedded image (wherein R2, R3, R4, X, Y and A are as described above).

Reaction [K] 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 - 2
The temperature is 0 to +100°C, preferably 0 to 40°C, and the reaction time is 0.01 to 100 hours, preferably 0.1 to 24 hours.

[0024]The reaction conditions for each reaction [G] to [K], such as reaction temperature, reaction time, solvent (solvent used as necessary), basic substance, etc., are usually similar unless otherwise specified. It can be appropriately selected depending on the reaction conditions in the reaction.

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

The sulfonamide compounds represented by the general formula (I) include those that exhibit a wide herbicidal spectrum at low doses and are safe against wheat, as shown in the test examples below. - When applying the herbicide of the present invention containing a sulfonamide compound represented by general formula (I) or a salt thereof as an active ingredient, a carrier, if necessary a diluent, a solvent, an emulsifier, a spreading agent, Mixed with various auxiliary agents such as surfactants, it can be used as granules, hydrated granules, wettable powders, emulsions, liquids, etc.
It is used by formulating it into a suspension. The appropriate blending weight ratio of the active ingredient compound and the pesticide adjuvant is generally 1:99 to 9.
The ratio is 0:10, preferably 5:95 to 80:20. Although the appropriate amount of the active ingredient to be used cannot be determined unconditionally due to differences in weather conditions, soil conditions, drug formulation, type of target weed, application period, etc., the amount of the active ingredient to be applied per area is generally from 0.005 g to 0.005 g. 50g, preferably 0.
The amount is 0.01 g to 10 g, more preferably 0.05 g to 5 g.

Examples of formulations of the herbicide of the present invention are described below. Formulation Example 1 (1) Compound No. 3
75 parts by weight (2) Demol EP
Powder 13.5 parts by weight (product name: Kao Corporation) (3) NaCl
10 parts by weight (4) Dextrin
0.5 parts by weight (5) TP-89121
1 part by weight (product name: Takemoto Yushi Co., Ltd.) Put each of the above ingredients into a high-speed mixing granulator, and then add 2 parts to it.
Add 0% water, granulate and dry to obtain a granular wettable powder.

Formulation Example 2 (1) Kaolin
83 parts by weight (2) Labelin S
2 parts by weight (Product name: Daiichi Kogyo Seiyaku (
(3) Solpol 5039
5 parts by weight (product name: manufactured by Toho Chemical Industry Co., Ltd.) (4) Carplex
10 parts by weight (trade name: manufactured by Shionogi & Co., Ltd.) A mixture of the above components (1) to (4) and compound No. 2
A wettable powder is obtained by mixing these in a weight ratio of 9:1.

Formulation Example 3 (1) Diatomaceous earth
63 parts by weight (2) Dixsol W-66
5 parts by weight (product name: Daiichi Kogyo Seiyaku Co., Ltd.) (3) Dixsol W-0913
2 parts by weight (Product name: Daiichi Kogyo Seiyaku Co., Ltd.)
(4) Compound No. 6
A wettable powder is obtained by mixing 30 parts by weight or more of each component.

Formulation Example 4 (1) High Filler No. 10
28 parts by weight (Product name: Matsumura Sangyo Co., Ltd.) (2) Solpol 5050
3 parts by weight (product name: manufactured by Toho Chemical Industry Co., Ltd.) (3) Solpol 5073
4 parts by weight (product name: manufactured by Toho Chemical Industry Co., Ltd.) (4) Carplex
5 parts by weight (trade name: manufactured by Shionogi & Co., Ltd.) (5) Compound No. 55
A wettable powder is obtained by mixing 60 parts by weight or more of each component.

Formulation Example 5 (1) Compound No. 39
4 Parts by weight (2) Corn oil 79
Weight part (3) Solpol 3815
15 parts by weight (product name: manufactured by Toho Chemical Industry Co., Ltd.) (4) Organic bentonite
2 parts by weight or more of (1) to (4)
) are mixed uniformly and pulverized with a Dyno Mill (manufactured by Willy & Verhohen Co., Ltd.) to obtain a suspension composition.

Formulation Example 6 (1) Compound No. 34
40 parts by weight (2) Solpol 72
90P 4
Parts by weight (Product name: Manufactured by Toho Chemical Industry Co., Ltd.) (3) Veegum
1.5 parts by weight (product name: Vanderbilt) (4) Propylene glycol
10 parts by weight (5) water

44.5 parts by weight or more of each component are uniformly mixed and wet-pulverized to obtain an aqueous suspension.

[0033] The herbicide of the invention can be mixed or used in combination with other agricultural chemicals, agricultural chemical auxiliaries, chemical damage 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]ethyl propionate (common name: quizalofopethyl) 3-(1-methylethyl)-(1H)-2,1,3-benzothiadiazine-4-(3H)- 1-2,2-dioxide (generic name: bentazone) ・5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-sodium nitrobenzoate (generic name: acifluorfen) ・2-[[ [[(4-chloro-6-methoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]
Ethyl benzoate (generic name: chlorimuronethyl: chl)
orimuron-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-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide (generic name: metolachlor)・(±)-2-[4-[(6-chloro-2-benzoxazolyl)oxy]phenoxy]ethyl 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 (generic 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 (common 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: imazethapyr) 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 (generic name: trifluralin)
・3-[(methoxycarbonyl)amino]phenyl
(3-methylphenyl)carbamate (generic name; phenmedipham) ・Ethyl [3-[[(phenylamino)carbonyl]oxy]phenyl]carbamate (common name; desmedipham) ・2-[4-[(3 -Methyl chloro-5-(trifluoromethyl)-2-pyridinyloxyphenoxypropionate (common name: haloxyfop), 5-amino-
4-chloro-2-phenyl-3-(2H)-pyridazinone (common name; chloridazone) 2-[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino [carbonyl]amino]sulfonyl]methylbenzoate (common name: metsulfuron-methyl) ・6-(4-isopropyl-4-methyl-5-oxo-
Methyl 2-imidazolin-2-yl)-m-toluate and methyl 2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-P-toluate (common name: imazametabenz)・1,2-dimethyl-3,5-diphenyl-1H-pyrazoline methyl sulfate (generic name: Difenzocort)
・3,6-dichloro-2-methoxybenzoic acid (common name;
dicamba) ・3,5-dibromo-4-hydroxybenzonitrile (
Generic name: Bromoxynil) ・4-Hydroxy-3,5-diiodobenzonitrile (
・2,4-dichlorophenoxyacetic acid (generic name: 2,4-
D-: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)

0036]・
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,
Methyl 5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]-2-thiophenecarboxylate (
Generic name: thiameturon-methyl: thiameturo
n-methyl)・(±)-2-[4-(2,4-dichlorophenoxy)phenoxy]methyl propionate (
・4-chloro-2-methylphenoxyacetic acid (generic name; MCPA) ・3,6-dichloro-2-pyridinecarboxylic acid (generic name: clopyralid) ・4-amino-3 , 5,6-trichloro-2-pyridinecarboxylic acid (common name: picloram)
O-(6-chloro-3-phenyl-4-pyridazinyl)
-S-octyl thiocarbamate (common name: pyridate)

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 mountain forests, farm roads, grounds, and factory sites. Application methods include soil treatment, foliage treatment, etc. You can choose as appropriate.

[0038]

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 5-chloro-N-[6-
[[[(4,6-dimethoxypyrimidin-2-yl)
Amino]carbonyl]amino]sulfonyl]pyridine-
2-yl]-N-methylvaleramide (compound No. 2-yl)
55) Synthesis of

1) N-tert-butyl-6-methylamino-2-pyridine sulfonamide 2.0 g, 1
, 2-dichloroethane 20 ml and triethylamine 0
．． 1.53 g of 5-chlorovaleryl chloride was added dropwise to 83 g of the mixture under ice cooling, and the mixture was reacted under reflux for 2 hours. Next, 1.53 g of 5-chlorovaleryl chloride was added to this, and the mixture was further reacted under reflux for 3 hours. After the reaction was completed, the reaction mixture was poured into water and extracted with methylene chloride. The extracted layer was washed with water and dried over anhydrous sodium sulfate. The residue obtained by distilling off the solvent was purified by silica gel column chromatography to obtain N-[6-[(tert-butylamino)sulfonyl]pyridin-2-yl]-5-chloro- with a melting point of 115-116°C. 2.8 g of N-methylvaleramide was obtained.

2) N-[6-[ obtained in step 1)
(tert-butylamino)sulfonyl]pyridine-
2-yl]-5-chloro-N-methylvaleramide 1.0
A mixture of g and 10 ml of trifluoroacetic acid was reacted at room temperature for 3 days. After the reaction was completed, the reaction mixture was concentrated under reduced pressure. A mixed solvent of ethyl acetate and n-hexane was added to the obtained residue, the precipitated solid was collected by filtration, and the melting point was 158-15.
N-[6-(aminosulfonyl)pyridine-2-
yl]-5-chloro-N-methylvaleramide was obtained.

3) N-[6-(
aminosulfonyl)pyridin-2-yl]-5-chloro-N-methylvaleramide 0.2 g, phenyl (4,
6-dimethoxypyrimidin-2-yl)carbamate 0
．． To a mixture of 2 g and 10 ml of acetonitrile was added 0.11 g of 1,8-diazabicyclo[5.4.0]-7-undecene under ice cooling, and the mixture was reacted at room temperature for 30 minutes. After the reaction was completed, the reaction mixture was poured into water, hydrochloric acid was added to make it weakly acidic, and the precipitated solid was collected by filtration. Wash this with water,
After drying, 0.23 g of the target product having a melting point of 121 to 122°C was obtained.

Synthesis Example 2 1,1,1-trifluoro-N-[6-[[[(4,6-dimethoxypyrimidin-2-yl)amino]carbonyl]amino]sulfonyl]pyridin-2-yl] -Synthesis of N-phenylacetamide (Compound No. 20 below)

1) A mixture of 2.0 g of N-tert-butyl-6-phenylamino-2-pyridinesulfonamide and 20 ml of trifluoroacetic acid was reacted at 50° C. for 2 hours. After the reaction was completed, the reaction mixture was concentrated under reduced pressure. A mixed solvent of ethyl acetate and n-hexane was added to the obtained residue, and the precipitated solid was collected by filtration to give a melting point of 154 to 156.
1.40 g of 6-phenylamino-2-pyridine sulfonamide was obtained.

2) 1.40 g of 6-phenylamino-2-pyridinesulfonamide obtained in step 1), phenyl (4,6-dimethoxypyrimidin-2-yl)
Add 1,8-diazabicyclo[5.4.0
]-7-Undecene (0.85 g) was added, and the mixture was reacted at room temperature for 1 hour. After the reaction was completed, the reaction mixture was poured into water, hydrochloric acid was added to make it weakly acidic, and the precipitated solid was collected by filtration. This was washed with water and dried to produce N-[
2.15 g of [(4,6-dimethoxypyrimidin-2-yl)amino]carbonyl]-6-phenylamino-2-pyridinesulfonamide was obtained.

3) N-[[(4
, 6-dimethoxypyrimidin-2-yl)amino]carbonyl]-6-phenylamino-2-pyridinesulfonamide, 10 ml of 1,2-dichloroethane, and 0.49 g of trifluoroacetic acid, and added 0.12 g of triethylamine. The mixture was added and reacted at room temperature for 1 hour. After the reaction was completed, the reaction mixture was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography to give a melting point of 16.
0.27 g of the target product having a temperature of 0 to 164°C was obtained.

Next, regarding the starting materials of Synthesis Example 1,
A specific example of its synthesis will be described. Synthesis Example 3 Synthesis of N-tert-butyl-6-methylamino-2-pyridinesulfonamide

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. Into this, in about 1 hour, 230.4g of benzyl mercaptan
was dripped. 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 1,000 ml of water and extracted with methylene chloride. 10 extraction layers
% aqueous sodium hydroxide solution, then water, and dried over anhydrous sodium sulfate. After drying, the solvent was distilled off to obtain 430 g of oily 2-benzylthio-6-chloropyridine.

2) A mixed solution of 430 g of 2-benzylthio-6-chloropyridine, 500 ml of acetic acid and 900 ml of water was ice-cooled and reacted by introducing an excess amount of chlorine gas at 0 to 5°C. After the reaction was completed, nitrogen gas was bubbled into the reaction system to remove excess chlorine gas. The reaction product was poured into ice water and extracted with methylene chloride. The extracted layer was washed with ice water and then dried over anhydrous sodium sulfate. Next, the methylene chloride solution was cooled on ice, and 401 g of tert-butylamine was added to about 2
It was added dropwise over a period of time to react. After the reaction was completed, the reaction mixture was poured into water and separated. The methylene chloride layer was dried over anhydrous sodium sulfate, and the methylene chloride was distilled off. A mixed solution of ether and n-hexane was added to the residue, and the precipitated 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
The mixture was placed in a 00ml mini autoclave and reacted at 150°C for about 3 hours. After the reaction is completed, the reaction mixture is allowed to cool,
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 with a melting point of 157-160°C.
I got it.

[0051] General formula (I) produced according to the above synthesis example
Representative examples of compounds represented by I-1) are listed in Table 1.

[0052]

[Table 1]

[0053]

[Table 2]

[0054]

[Table 3]

[0055]

[Table 4]

[0056]

[Table 5]

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

[0058]

[Table 6]

[0059]

[Table 7]

[0060]

[Table 8]

[0061]

[Table 9]

[0062]

[Table 10]

[0063]

[Table 11]

Test Example 1 Upland soil was filled in a 1/1,500 are pot, and seeds of various plants were sown. After that, the plants are grown at a certain leaf age (rice 1.2-3.5 leaf stage, soybean primary leaf stage - 1.2 leaf stage, maize 2.0-3.5 leaf stage, cotton cotyledon stage - 1.0 leaf stage,
Wheat 2.0 to 2.8 leaf stage, Japanese fir 0.3 to 3.1 leaf stage, morning glory 0.2 to 2.1 leaf stage, golden deer cotyledon to 2.0 leaf stage, blueberry 0.1 to 2 leaf stage 0 leaf stage, barnyard grass 1.7 to 3.5 leaf stage, and Japanese barley 1.6 to 2.0 leaf stage), weigh out the hydrating agent of the herbicide of the present invention to a predetermined amount, Diluted in 5 liters of water per cup. 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. 18 to 38 days after treatment, the growth status of various plants was visually observed and investigated.
The degree of growth inhibition was evaluated on a scale of 0 (1: same as untreated plot to 10: completely inhibited), and the results shown in Table 3 were obtained.

[0065]

[Table 12]

[0066]

[Table 13]

[0067]

[Table 14]

[0068]

[Table 15]

[0069]

[Table 16]

[0070]

[Table 17]

[0071]

[Table 18]

Test Example 2 Upland soil was filled in a 1/10,000 are pot, and wheat and wild oat seeds were sown in separate pots. Thereafter, when wheat reached the 1.8-3.0 leaf stage and wild oat reached the 1.1-2.0 leaf stage, a predetermined amount of the hydrating agent of the herbicide of the present invention was weighed and Diluted in 5 liters of water per serving. 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 23rd to 24th days 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 4 were obtained.

[0073]

[Table 19]

Claims (4)

[Claims] Claim 1: General formula (I) [Formula 1] (wherein, R1 is a haloalkyl group, an alkenyl group, or a haloalkoxy group, and R2 is a hydrogen atom, an alkyl group, a haloalkyl group, a cycloalkyl group, a phenyl group, or is a benzyl group, R3 is a hydrogen atom, a halogen atom, an alkyl group, or a haloalkyl group, X and Y are each independently a halogen atom, an alkyl group, an alkoxy group, or a haloalkoxy group, and A is =CH- or =N-) or a salt thereof. Claim 2: General formula (II) [Formula 2] (wherein, R1 is a haloalkyl group, alkenyl group, or haloalkoxy group, and R2 is a hydrogen atom, an alkyl group, a haloalkyl group, a cycloalkyl group, a phenyl group, or is a benzyl group, R3 is a hydrogen atom, a halogen atom, an alkyl group or a haloalkyl group, and Z1 is an -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) atom, alkyl group, alkoxy group or haloalkoxy group, A is =CH- or =N-, Z2 is -NH2 group when Z1 is -NCO group or -NHCO2R4 group, Z1 is -NH2 group is a -NCO group or -NHCO2R4 group, R4 is as described above).
I) A method for producing a sulfonamide compound or a salt thereof represented by the following formula: (wherein R1, R2, R3, X, Y and A are as described above). Claim 3: General formula (I) [Formula 1] (wherein, R1 is a haloalkyl group, alkenyl group, or haloalkoxy group, and R2 is a hydrogen atom, an alkyl group, a haloalkyl group, a cycloalkyl group, a phenyl group, or is a benzyl group, R3 is a hydrogen atom, a halogen atom, an alkyl group, or a haloalkyl group, X and Y are each independently a halogen atom, an alkyl group, an alkoxy group, or a haloalkoxy group, and A is =CH- or =N-) or a salt thereof as an active ingredient. [Claim 4] General formula (II-1) [Formula 4] (wherein, R1 is a haloalkyl group, an alkenyl group, or a haloalkoxy group, and R2 is a hydrogen atom, an alkyl group, a haloalkyl group, a cycloalkyl group, or a phenyl group) or benzyl group, and R3 is a hydrogen atom, a halogen atom, an alkyl group or a haloalkyl group).