CN1016661B - Herbicidal composition containing pyridine sulfonamide - Google Patents

Abstract

The present invention relates to a herbicidal composition comprising a herbicidally effective amount of a compoundA compound of the formula or a salt thereof and an agricultural adjuvant.

Description

The present invention relates to novel, substituted pyridinesulfonamide compounds and salts thereof, herbicides containing such compounds as active ingredients, and processes for preparing such compounds.

The substituted pyridinesulfonamide compound of the present invention is characterized in that the pyridine ring has an N-substituted (ie, there is a substituent on the nitrogen atom) aminocarbonyl group. This substituted pyridinesulfonamide compound is known from the general formulas disclosed in U.S. Patent No. 4,518,776, European Patent Application Publication No. 101670 and U.S. Patent No. 4,521,597, but the present invention Substituted pyridinesulfonamides are not specifically disclosed in the above-mentioned prior patent documents. U.S. Patent No. 4,435,206 describes a substituted pyridinesulfonamide compound, but the compound does not have an N-substituted aminocarbonyl group on the pyridine ring. People have developed many similar herbicides with sulfonamide compounds as active ingredients, but have not yet developed a herbicide that is both highly safe for cereals and has a good herbicidal effect.

The inventors of the present invention have intensively studied the relationship between the chemical structure and physiological activity of sulfonamide compounds. In particular, the inventors conducted further research in order to find a herbicide for cereals. As a result, the inventors have come to the conclusion that there is a pyridine sulfonamide compound that is an effective herbicide that can be used in grain fields. The compound has a pyridine ring with an N-substituted aminocarbonyl group and a special substituents (if any), the compound also has a sulfonamide moiety with a pyrimidin-2-ylaminocarbonyl substituted on the nitrogen atom of the moiety; the inventors thus made This invention.

The present invention provides a substituted pyridinesulfonamide compound, its salt, herbicide containing them and their preparation method. This substituted pyridinesulfonamide compound can be represented by the following general formula:

（R3和R4各自独立地代表一个氢原子或烷基）;n为0或整数1或2;X1和X2各自独立地代表一个甲基、甲氧基或乙氧基。R1 and R2 independently represent a hydrogen atom, alkyl, haloalkyl, alkenyl, alkynyl, alkoxy, haloalkoxy, alkoxyalkyl, haloalkoxyalkyl, cycloalkyl, halocycloalkyl , alkoxycarbonyl, haloalkoxycarbonyl, phenyl or halophenyl, provided that when one of R1 and R2 represents a hydrogen atom, the other represents a group other than a hydrogen atom in the above groups; R1 and R2 can form a heterocyclic ring together with an adjacent nitrogen atom; Y represents a halogen atom, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkoxyalkyl, haloalkoxy Alkyl or group

(R3 and R4 each independently represent a hydrogen atom or an alkyl group); n is 0 or an integer of 1 or 2; X1 and X2 each independently represent a methyl, methoxy or ethoxy group.

The salts of the substituted pyridinesulfonamide compounds of the present invention include alkali metal salts (such as sodium salt and potassium salt), alkaline earth metal salts (such as magnesium salt and calcium salt) and amine salts (such as monomethylamine salt, dimethylamine salt and triethylamine salt). These salts can be prepared by conventional methods.

In the general formula (I), the halo represented by R1 and R2 Alkyl, haloalkoxy, haloalkoxyalkyl, haloalkoxycarbonyl, halocycloalkyl or halophenyl, and haloalkyl, haloalkoxy, haloalkylthio or haloalkoxyalkyl represented by Y can be represented by One or more halogen atoms are substituted.

The alkyl or alkyl part represented by R1, R2, R3, R4 and Y in the general formula (I) is an alkyl group containing 1-6 carbon atoms, such as methyl, ethyl, propyl and butyl . The alkenyl or alkenyl moiety represented by R1 and R2 has 2 to 6 carbon atoms, such as propenyl and butenyl. Alkynyl or alkynyl moieties have 2-6 carbon atoms, eg propynyl and butynyl. Said cycloalkyl group has 3 to 6 carbon atoms and is exemplified by cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The halogen atom in R1, R2 and Y is, for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. R1 and R2 together with said nitrogen atom may form a heterocyclic ring. Examples of such heterocycles are morpholine ring, aziridine ring, pyrrolidine ring and piperidine ring.

Among the substituted pyridinesulfonamide compounds represented by the general formula (I), compounds represented by the following general formula and their salts are preferred:

More preferred specific compounds are described below:

(1) R1 represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group, and R2 represents an alkyl group, preferably a methyl group.

(2) Y represents a halogen atom, alkyl, haloalkyl, alkoxy or alkoxyalkyl, preferably a chlorine atom, bromine atom, methyl or difluoromethyl, each of which is attached to the pyridine nucleus 6 bits, and n is 0, 1 or 2, preferably 0 or 1.

(3) X1 and X2 each independently represent a methoxy group.

(4) More specifically, the following compounds are preferred:

N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-3-methylaminocarbonyl-2-pyridinesulfonamide or N-[(4,6-dimethoxypyrimidine-2- base)aminocarbonyl]-3-dimethylaminocarbonyl-2-pyridinesulfonamide, or 6-chloro(or bromo, difluoromethyl or methyl)-N-[(4,6-dimethoxypyrimidine- 2-yl)aminocarbonyl]-3-dimethylaminocarbonyl-2-pyridinesulfonamide.

According to the present invention, the substituted pyridinesulfonamide compounds represented by the general formula (I) and salts thereof can be prepared by the following methods.

A pyridine compound represented by general formula (II) is reacted with a pyrimidine compound represented by general formula (III),

In formula (II), R is as defined above, and Z1 represents a group _-NH2 , -NCO, -NHCOCl or -NHCOOR5 (wherein R5 represents an alkyl or aryl group); in formula (III), X3 and X4 are each Independently represent a halogen atom, methyl, methoxy or ethoxy, Z2 represents the group -NH ₂ , -NCO, -NHCOCl or -NHCOOR5 (where R5 is as defined above), provided that when Z1 represents the group -NH ₂ , Z2 represents the group-NCO,-NHCOCl or-NHCOOR5; and when Z2 represents the group- _NH2 , Z1 represents the group-NCO,-NHCOCl or-NHCOOR5. After that, if X3 and/or X4 are halogen atoms, methoxylation or ethoxylation is carried out. In addition, a salt-forming treatment is performed when necessary.

More specifically, the above-mentioned pyridinesulfonamide compounds and derivatives thereof can be produced by the methods [A] to [G] (see Fig. 1).

You can also use the following methods:

[H] R-SO ₂ NHCONH ₂ + (Ⅲ-4) (130～250℃)/(0.5～24 hours) (Ⅰ)

(Ⅱ-6)

In the reaction equations of methods [A] to [H], Hal represents a halogen atom, and R, R5, X1, X2 and X3 are as defined above. The compounds represented by the general formula (II-5) can be produced by the steps of methods [A] to [F]. The compound represented by the general formula (II-6) can be easily prepared by reacting the compounds represented by the general formulas (II-2) to (II-4) with ammonia. The aryl group represented by R5 in the general formulas (III-1) and (II-2) may be naphthyl or phenyl which may be substituted by one or more chlorine atoms or one or more methyl groups. In methods [A] and [D], if necessary, 1,8-diazabicyclo[5.4.0]undec-7-ene may be added to accelerate the reaction. In methods [B], [C], [E] and [F], 1,4-diazabicyclo[2.2.2]octane can be added if necessary, and in methods [B], [C], In [E] and [F], a base such as triethylamine or pyridine may be added if necessary. When using convenience [A] to [H], it can be carried out in a solvent if necessary. Examples of solvents are: aromatic hydrocarbons (such as benzene, toluene, xylene, and chlorobenzene), cyclic or acyclic aliphatic hydrocarbons (such as chloroform, tetrahydrocarbon, dichloromethane, dichloroethane, trichloroethane, hexane and cyclohexane), ethers (such as diethyl ether, dioxane, and tetrahydrofuran), nitriles (such as acetonitrile, propionitrile, and propylene Nitriles) and polar aprotic solvents such as dimethylsulfoxide (DMSO) and sulfolane).

(1) According to the diagram: the pyridine compound (II-1') in the general formula (II-1) used as the raw material of the reaction formula can be prepared according to the methods indicated in Routes 1 and 2 (see later).

(2) According to the diagram (route 3), if Y in the general formula (II-1') is an alkyl group substituted by one or more fluorine atoms, then the corresponding product can also be prepared by the method indicated in the following route 3 (See the picture after the text).

According to the method of route 1 and 2 in the system. Q1 is a hydrogen atom or a halogen atom, NBS is N-bromosuccinimide, and Rui BPO is benzoyl peroxide. The meanings of other abbreviations and symbols are the same as above.

(3) According to the diagram (route 4), when Y in the general formula (II-1') is an alkoxy group, a haloalkoxy group, an alkylthio group or a haloalkylthio group, the corresponding product can also be obtained according to the following route 4 Prepared according to the method shown (see the figure below).

(4) According to the illustration (route 5), when Y in the general formula (II-1') is alkoxymethyl or haloalkoxymethyl, the corresponding product can also be prepared according to the method shown in the following route 5 ( See the picture after the text).

时，相应产品也可由以下路线6所示的方法制得（图见文后）。(5) According to the diagram (Route 6), when Y in the general formula (II-1') is a group

, the corresponding product can also be prepared by the method shown in the following route 6 (see the figure below).

(6) According to the diagram (route 7), when Y in the general formula (II-1') is a halogen atom, the corresponding product can also be prepared by the method shown in the following route 7 (see the figure below).

(7) According to the diagram (Scheme 8), the 3-pyridinesulfonamide compound represented by the general formula (II-1') can also be prepared by the method shown in the following Scheme 8 (see the figure below).

(8) According to the diagram (Route 9), the N-pyridine oxide compound represented by the general formula (II-1") can also be prepared by the method shown in the following Route 9 (see the figure below).

(9) According to the diagram (route 10), each compound represented by the general formula (II-2) to (II-4) can be prepared from each compound represented by the general formula (II-1) according to the method of the following route 10 (See the picture after the text).

The reaction conditions for producing the starting compound, such as reaction temperature, reaction time, optionally used solvent, basic substance, etc., can be appropriately selected in accordance with conventional reaction conditions of similar reactions.

Described below are synthesis examples of intermediates of the compounds of the present invention.

Intermediate Synthesis Example 1

Synthesis of 2-aminosulfonyl-5-chloro-N,N-dimethylnicotinamide

[I] 6.5 g of 2,5-dichloronicotinic acid was mixed with 24.7 ml of thionyl chloride and reacted therewith for 2 hours under reflux. After the reaction, excess thionyl chloride was distilled off, and 39 ml of methylene chloride was added to the mixture, followed by 2.77 g of dimethylamine hydrochloride. 8.60 g of triethylamine was added dropwise over a period of about 1 hour, and the resulting mixture was allowed to react at room temperature for about 1 hour.

After the reaction was completed, the reaction product was poured into water and extracted with dichloromethane. The dichloromethane layer was dried with sodium sulfate, and the dichloromethane was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography to obtain 5.5 g of 2,5-dichloro-N,N-dimethylnicotinamide, melting point 120-122°C.

[II] At 80°C for about 1 hour, mix 3.0 g of 2,5-dichloro-N,N-dimethylnicotinamide prepared by method [I], 1.70 g of benzyl mercaptan and 5 ml of dimethyl The mixture of sulfoxides was added dropwise to a suspension of 1.89 g of anhydrous potassium carbonate in 28 ml of dimethylsulfoxide. The resulting mixture was reacted at 130-140°C for 30 minutes.

After the reaction was completed, the reaction product was added into water and extracted with dichloromethane. The dichloromethane layer was dried over anhydrous sodium sulfate, and the dichloromethane was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography to obtain 2.18 g of 2-benzylthio-5-chloro-N,N-dimethylnicotinamide as an oil.

[Ⅲ] Chlorine gas was bubbled into 20 ml of a 50% acetic acid solution containing 2.36 g of 2-benzylthio-5-chloro-N,N-dimethylnicotinamide at 0-5°C. The reaction was stopped when excess chlorine evolved.

After the reaction was completed, the reaction product was added to 150 g of ice and 200 ml of dichloromethane, and the dichloromethane layer was separated. The dichloromethane layer was washed with 300 ml of ice water and allowed to cool to 0°C. Then tert-butylamine was added dropwise, and the resulting mixture was stirred until the temperature of the layer reached room temperature. The reaction solution is weakly alkaline after inspection, and the reaction has been completed so far.

After the reaction was completed, the reaction product was added to water and extracted with dichloromethane. The dichloromethane layer was separated and dried over anhydrous sodium sulfate; the dichloromethane was distilled off. The resulting residue was purified by silica gel column chromatography to obtain 1.21 g of 2-tert-butylaminosulfonyl-5-chloro-N-,N-dimethylnicotinamide, melting point 143-145°C.

[Ⅳ] Add 1.0 g of 2-tert-butylaminosulfonyl-5-chloro-N,N-dimethylnicotinamide prepared by method [Ⅲ] to 10 ml of trifluoroacetic acid, and let the two under reflux conditions React for about 1 hour. After the reaction was completed, the trifluoroethylene in the reaction product was evaporated under reduced pressure. acid. The resulting residue was purified by silica gel column chromatography to obtain 0.71 g of 2-aminosulfonyl-5-chloro-N,N-dimethylnicotinamide having a melting point of 155-157°C.

Intermediate Synthesis Example 2

Synthesis of 2-aminosulfonyl-6-chloro-N,N-dimethylnicotinamide

[I] At 130-140°C, in about 1 hour, 7.0 g of 2,6-dichloronicotinic acid was prepared according to the same steps in the process [I] in Example 1 of Intermediate Synthesis 2,6- Dichloro-N, N-dimethylnicotinamide) (melting point 62.5-65 ° C), 3.8 g of benzyl alcohol and 20 ml of dimethyl sulfoxide was added dropwise to 6.6 g of anhydrous potassium carbonate in 50 ml of dimethyl sulfoxide The resulting mixture was allowed to react at 150° C. for about 2 hours.

After the reaction was completed, the reaction product was added to water and extracted with dichloromethane. The dichloromethane layer was dried over anhydrous sodium sulfate, and the dichloromethane was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography to obtain 6.0 g of oily 6-benzyloxy-2-chloro-N,N-dimethylnicotinamide.

[II] With 0.69 g of 6-benzyloxy-2-chloro-N, N-dimethylnicotinamide, the 6-benzyloxy group prepared according to the same steps of the process [II] in Example 1 of Intermediate Synthesis -2-Benzylthio-N,N-dimethylnicotinamide (oily product) was mixed with 6 ml of concentrated hydrochloric acid, and the resulting mixture was allowed to react at room temperature for about 15 hours with stirring.

After the reaction was completed, the reaction product was added to water, and the desired product was extracted with dichloromethane. The dichloromethane layer was dried over anhydrous sodium sulfate, and the dichloromethane was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography to obtain 0.41 g of 2-benzylthio-N,N-dimethyl-6-hydroxynicotinamide, melting point 52-60°C.

[Ⅲ] Add 1.0 g of 2-benzylthio-N,N-dimethyl-6-hydroxynicotinamide and 0.3 ml of dimethylformamide prepared in the above procedure [II] to 5 ml of thionyl chloride , and react the resulting mixture under reflux for about 1 hour.

After the reaction was completed, the reaction product was added to water, and the desired product was extracted with dichloromethane. The dichloromethane layer was washed with water and dried over anhydrous sodium sulfate. Dichloromethane was distilled off under reduced pressure, and the resulting residue was purified by silica gel chromatography to obtain 0.45 g of 2-benzylthio-6-chloro-N,N-dimethylnicotinamide as an oil.

[Ⅳ] Using the above product, and following the same steps of [Ⅲ] and [Ⅳ] in Intermediate Synthesis Example 1, 2-aminosulfonyl-6-chloro-N, N-dimethylnicotinamide was obtained , melting point 171-173°C.

Intermediate Synthesis Example 3

Synthesis of 2-aminosulfonyl-N,N-dimethyl-6-ethoxynicotinamide

[I] 0.231 g of sodium metal was added to 50 ml of absolute ethanol to prepare a sodium ethoxide ethanol solution. In this solution, add 2.0 grams of 2,6-dichloro-N, N-dimethylnicotinamide obtained by the same step of process [I] in Example 1 of Intermediate Synthesis, and allow the mixture to react under reflux conditions about 1 hour. The reacted solution was added to water and extracted with dichloromethane. The disulfide layer was dried over anhydrous sodium sulfate, and dichloromethane was distilled off under reduced pressure. The residue was purified by silica gel chromatography to obtain 1.95 g of 2-chloro-N,N-dimethyl-6-ethoxynicotinamide as an oil.

[II] Use the above-mentioned product to operate according to the same steps in the processes [II], [III] and [IV] in Example 1 of intermediate synthesis to obtain 2-aminosulfonyl-N,N- Dimethyl-6-ethoxynicotinamide.

Intermediate Synthesis Example 4

Synthesis of 2-aminosulfonyl-N,N-dimethyl-6-fluoronicotinamide

[I] Add 0.302 g of 2-tert-butylaminoiodide-6-chloro-N, N-dimethylnicotinamide to 10 ml of dimethylformamide slurry containing 0.116 g of spray-dried Potassium fluoride; the resulting mixture was then reacted at 150°C for about 3 hours with stirring.

After the reaction, the reaction solution was added to 100 ml of water, and extracted with dichloromethane. The extract was washed repeatedly with water and dried over anhydrous sodium sulfate. Dichloromethane was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 0.204 g of 2-tert-butylaminosulfonyl-N,N-dimethyl-6-fluoronicotinic acid amide.

[II] Using the above product, follow the same steps as in the process [IV] in Example 1 of Intermediate Synthesis to obtain 2-aminosulfonyl-N,N-dimethyl-6-fluorofume with a melting point of 164-165°C amides.

Intermediate Synthesis Example 5

Synthesis of 2-aminosulfonyl-N-methylnicotinamide

[I] 250 ml of dry methanol was saturated with hydrogen chloride gas, and then 250 ml of methanol and 30 g of 2-mercaptonicotinic acid were added thereto. The resulting solution was allowed to react overnight at room temperature.

After the reaction, the reaction solution was made weakly alkaline with ammonia gas, and methanol was distilled off under reduced pressure. The resulting crystals were then washed with water and filtered off. The filtered crystals were dried under reduced pressure to obtain 24 g of methyl 2-mercaptonicotinate with a melting point of 136-140°C.

[II] Add 10 g of methyl 2-mercaptonicotinate prepared by the process [I] to the suspension prepared with 50 ml of acetic acid and 50 ml of water middle. Chlorine gas is introduced into the reaction system at a temperature of 0°C or lower, and the reaction is completed when excess chlorine gas escapes.

After the reaction, the resulting solution was added to a mixture of 150 g of ice and 500 ml of dichloromethane, and the dichloromethane layer was separated. The dichloromethane layer was washed with 500 ml of ice water and cooled to 0°C. Subsequently, 12.9 g of t-butylamine was added dropwise to the above solution, and stirred until the temperature of the resulting solution reached room temperature. After stirring, the reaction solution was added to 500 ml of water, followed by extraction with dichloromethane. After drying over anhydrous sodium sulfate and distilling off methylene chloride, 13 g of crude crystals were obtained. The crystals were recrystallized from dichloromethane and n-hexane to obtain methyl 2-tert-butylaminosulfonylnicotinate, with a melting point of 169-171°C.

[III] 1 g of the above product was added to 20 ml of anhydrous methanol to which excess methylamine had been absorbed, followed by stirring for 15 hours.

After the reaction was completed, the reaction product was added to water, and extracted with dichloromethane. After extraction, the dichloromethane layer was dried with anhydrous sodium sulfate, and the dichloromethane was distilled off under reduced pressure to obtain 0.73 g of 2-tert-butylaminosulfonyl-N-methylnicotinamide, with a melting point of 189°C-192°C.

[Ⅳ] Using this product, follow the same steps as in the process [Ⅳ] in the intermediate synthesis example 1 to obtain 2-aminosulfonyl-N-methylnicotinamide with a melting point of 207-209.5°C.

Intermediate Synthesis Example 6

Synthesis of 2-aminosulfonyl-N,N-dimethylnicotinamide

[Method A]

[I] In a nitrogen atmosphere, at 10°C or lower, add 10 ml of n-hexane containing 19% trimethylaluminum to the following solution: 1.3 ml of dimethylamine dissolved in obtained in 10 ml of anhydrous benzene. The resulting mixture was allowed to react until its temperature reached room temperature. A solution obtained by dissolving methyl 2-tert-butylaminosulfonynicotinate in 40 ml of benzene and 20 ml of methylene chloride was dropped into the reaction solution, and the resulting mixture was stirred under reflux for about 9 hours.

After the reaction, the reaction solution was added to dilute hydrochloric acid, and extracted with dichloromethane. The extract was dried over anhydrous sodium sulfate, dichloromethane was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 1.0 g of 2-tert-butylaminosulfonyl-N,N-dimethylnicotinamide.

[II] Using the above product, follow the same steps as in the process [IV] in the intermediate synthesis example 1 to obtain 2-aminosulfonyl-N,N-dimethylnicotinamide with a melting point of 209-211°C.

[Method B]

Chlorine gas was bubbled into a solution of 2.7 g of 2-benzylthio-N,N-dimethylnicotinamide in 50 ml of 50% acetic acid until excess chlorine gas evolved.

After the reaction, the reaction mixture was added to 200 ml of ice water and extracted with 60 ml of dichloromethane. The dichloromethane layer was then washed with 100 ml of ice water while cooling it to 0°C. Ammonia gas was introduced into the solution until it was transformed into an alkaline solution. After dichloromethane was distilled off, 15 ml of water was added to the residue, and the resulting mixture was stirred. The resulting crystals were filtered off and washed with a little water. The crystals were dried under reduced pressure to obtain 1.27 g of 2-aminosulfonyl-N,N-dimethylnicotinamide with a melting point of 209-211°C.

Intermediate Synthesis Example 7

Synthesis of 2-aminosulfonyl-N-ethyl-N-methylnicotinamide

[I] A mixture of 30 g of 2-chloronicotinic acid and thionyl chloride was reacted for 4 hours under reflux. After the excess thionyl chloride in the reaction solution was evaporated under reduced pressure, 500 ml of dichloromethane was added to the reaction solution, and methylamine gas was introduced at room temperature until the reaction solution became a weakly alkaline solution. The formed methylamine hydrochloride was filtered off and the filtrate was concentrated. The precipitated crystals were recrystallized from n-hexane and dichloromethane to obtain 27 g of 2-chloro-N-methylnicotinamide, melting point 106-107°C.

[II] At 0-5°C, a solution of 5 g of 2-chloro-N-methylnicotinamide prepared in the same step as process [I] in this example in 10 ml of dimethylformamide was added dropwise to In the suspension prepared by adding 117 g of 60% sodium hydride in 50 ml of dimethylformamide. The resulting mixture was reacted at 0-5°C for about 30 minutes, and then 3.5 g of bromoethane was added dropwise at 0°C. The resulting solution was reacted at room temperature for 2.5 hours. The reaction solution was then added to water, and extracted with dichloromethane. The extract was washed with water and dried over anhydrous sodium sulfate. Then dichloromethane was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 5.7 g of 2-chloro-N-ethyl-N-methylnicotinamide as an oil.

[Ⅲ] Use this product to operate in the same steps as in the process [II] to [IV] in the intermediate synthesis embodiment 1 to obtain 2-aminosulfonyl-N-ethyl-N-methylnicotinamide, whose melting point is 202-203°C.

Intermediate Synthesis Example 8

Synthesis of 2-aminosulfonyl-N,N-dimethyl-6-methylnicotinamide

[I] A drop of dimethylformamide was added to a mixture of 1.35 g of 2-hydroxy-6-methylnicotinic acid and 15 ml of thionyl chloride, and the resulting solution was allowed to react for about 2 hours under reflux. Excess thionyl chloride was distilled off under reduced pressure, and 50 ml of dichloromethane was added to the residue. The resulting mixture was added dropwise to a mixture of 30 ml of a 30% aqueous dimethylamine solution and 50 ml of methylene chloride, and the resulting solution was allowed to react at room temperature for 15 minutes.

After the reaction was completed, the reaction mixture was added to water and extracted with dichloromethane. The dichloromethane layer was washed with water and dried over anhydrous sodium sulfate. The dichloromethane was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 1.57 g of 2-chloro-3-N,N-dimethylaminocarbonyl-6-picoline (melting point 66-67.5°C).

[II] Use this product to operate according to the same steps as in the process [II] to [IV] in Example 1 of Intermediate Synthesis to obtain 2-aminosulfonyl-N, N-dimethyl- 6-Methylnicotinamide.

Intermediate Synthesis Example 9

Synthesis of 2-aminosulfonyl-N,N-dimethyl-6-methoxynicotinamide

[I] 33 g of 2,6-dichloronicotinic acid and 100 ml of thionyl chloride were mixed and reacted under reflux for about 3 hours.

After the reaction was completed, excess thionyl chloride was distilled off under reduced pressure, and 500 ml of dichloromethane was added. To this mixture was added dropwise anhydrous methanol at a temperature ranging from room temperature to 40°C. After the dropwise addition was complete, the resulting mixture was allowed to reflux for about 1 hour.

After completing the reaction, the reaction solution was added to 500 ml of water, and then separated with dichloromethane. After the dichloromethane layer was washed with water and dried over anhydrous sodium sulfate, the dichloromethane was distilled off under reduced pressure. The residue was purified by silica gel column chromatography to obtain 27 g of methyl 2,6-dichloronicotinate, melting point 45.5-48.0°C.

[II] Use the above products according to the process [I] in the intermediate synthesis example 3, the process [II] in the intermediate synthesis example 1, [method A] and [I] and the intermediate synthesis in the intermediate synthesis example 6 The same steps as the steps [III] to [IV] in Example 1 were carried out to obtain 2-aminosulfonyl-N,N-dimethyl-6-methoxynicotinamide.

Intermediate Synthesis Example 10

Synthesis of 2-aminosulfonyl-6-difluoromethyl-N,N-dimethylnicotinamide

[I] The mixture of the following substances was heated to reflux for 3 hours: 11.5 grams of 2-tert-butylaminosulfonyl-6-methyl fume produced by the same steps of process [I] and [II] in Example 5 of Intermediate Synthesis methyl ester, 186 ml carbon tetrachloride, 14.84 g N-bromosuccinimide and 0.68 g benzoyl peroxide.

After the reaction was completed, the reaction mixture was filtered, and the filtrate was concentrated and purified by silica gel column chromatography to obtain 4.5 g of methyl 2-tert-butylaminosulfonyl-6-dibromomethylnicotinate.

[II] 3.7 g of silver nitrate was added to a mixture consisting of 4.4 g of the above product, 35 ml of ethanol and 29 ml of water, and the resulting mixture was heated under reflux for 3 hours.

After the reaction, the reaction mixture was added to water and extracted with dichloromethane. The extract was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off. The residue was purified by silica gel column chromatography to obtain 2.92 g of methyl 2-tert-butylaminosulfonyl-6-formylnicotinate.

[Ⅲ] A solution of 0.642 g of diethylaminosulfur trifluoride in 5 ml of dichloromethane was added to a solution of 0.48 g of 2-tert-butylaminosulfonyl-6-formylnicotinic acid methyl ester in 19 ml of dichloromethane. solution, and the mixture was stirred at room temperature for 1 hour.

After the reaction, the reaction mixture was added into water and extracted with dichloromethane. (Dichloromethane layer) was washed with water and dried over anhydrous sodium sulfate. The solvent was then distilled off. The residue was purified by silica gel column chromatography to obtain 0.25 g of methyl 2-tert-butylaminosulfonyl-6-dichloromethylnicotinate.

[IV] A mixture consisting of 0.50 g of the above product and 10 ml of anhydrous methanol saturated with dimethylamine was reacted overnight at room temperature.

After completion of the reaction, the solvent in the reaction mixture was distilled off, and then the residue was purified by silica gel column chromatography to obtain 0.15 g of 2-tert-butylaminosulfonyl-6-difluoromethyl-N,N-dimethylnicotinamide.

[Ⅴ] Using the above product, follow the same steps as in the process [Ⅳ] in the intermediate synthesis example 1 to obtain 2-aminosulfonyl-6-difluoromethyl-N,N-dimethylnicotinamide.

Intermediate Synthesis Example 11

Synthesis of 2-aminosulfonyl-6-bromo-N,N-dimethylnicotinamide

[I] 5 ml of acetic acid was added to 1.2 g of 2-benzylthio-6-chloro-N,N-dimethylnicotinamide, and the resulting mixture was heated to 70°C. Hydrogen bromide gas was bubbled into the mixture for 30 minutes, and the mixture was allowed to react for another 30 minutes.

After the reaction was completed, the reaction mixture was cooled and added to ice water, and extracted with dichloromethane. (Dichloromethane layer) was washed with sodium bicarbonate solution, then with water, and dried over anhydrous sodium sulfate. Dichloromethane was distilled off, and the residue was purified by silica gel column chromatography to obtain 1.0 g of 2-benzylthio-6-bromo-N,N-dimethylnicotinamide, melting point 105-106°C.

[II] Using the above product, follow the same steps of [III] and [IV] in Intermediate Synthesis Example 1 to obtain 2-aminosulfonyl-6-bromo-N, N-dimethylnicotinamide, The melting point is 154-156°C.

Typical examples of the compounds represented by the general formula (II-1') are summarized in Table 1.

Examples of synthesizing the compounds of the present invention are given below.

Synthesis Example 1

Synthesis of 5-chloro-N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-3-dimethylaminocarbonyl-2-pyridinesulfonamide (9 compounds)

Add 0.30 g of 2-aminosulfonyl-5-chloro-N, N-dimethylnicotinamide and 0.35 g of 2-phenoxycarbonylamino-4,6-dimethoxypyrimidine to 10 ml of anhydrous acetonitrile, To the resulting suspension was added 0.19 g of 1,8-diazabicyclo[5.4.0]undec-7-ene, and the resulting mixture was allowed to react at room temperature for 45 minutes.

After the reaction was completed, the reaction mixture was added to water, and the insoluble matter was filtered off. The solution was weakly acidified with concentrated hydrochloric acid, followed by extraction with dichloromethane. The solution was then dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain 0.26 g of the title compound, melting at 152-155°C.

Synthetic Examples 2-13

According to the same steps of Synthesis Example 1, the results are shown in Table 2.

Synthetic Example 14

Synthesis of N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-3-dimethylaminocarbonyl-2-pyridinesulfonamide

method 1

At 15°C, add dropwise a mixed solution of 250 mg of 2-amino-4,6-dimethoxypyridine, 0.65 g of triethylamine and 2.5 g of ethyl acetate to 6.3 ethyl acetate containing 20% phosgene solution, and then keep the composition at 15°C and react for 1 hour. The mixture was then heated to 90°C in an oil bath, and excess phosgene and ethyl acetate were distilled off. Then, a solution obtained by dissolving 300 mg of 2-aminosulfonyl-N,N-dimethylnicotinamide in 10 ml of acetonitrile was added dropwise to the above mixture, and 0.2 g of triethylamine was further added dropwise. The resulting mixture was reacted at room temperature for 1 hour.

After the reaction was completed, the product was added to water, the resulting solution was acidified with hydrochloric acid, and the precipitated crystals were filtered. The crystals were washed with water and dried to obtain 0.46 g of the title compound.

Method 2

[I] Add 2.13 g of 2-aminosulfonyl-N, N-dimethylnicotinamide at -5°C to 5 ml of dimethylformamide slurry containing 60% sodium hydride, and allow the resulting mixture to react for about 1 Hour. A solution of 2.14 g of diphenyl carbonate in 10 ml of dimethylformamide was added dropwise to the above solution at -5°C. The solution was warmed to room temperature over 30 minutes to complete the reaction. The reaction solution was added to water and washed with dichloromethane. The aqueous layer was acidified with hydrochloric acid, then extracted with dichloromethane. The dichloromethane layer was dried over anhydrous sodium sulfate, and the dichloromethane was distilled off under reduced pressure. The obtained crystals were recrystallized from ethyl acetate and hexane to obtain 0.91 g of N,N-dimethyl-2-phenoxycarbonylsulfonylnicotinamide, melting point 189-194°C.

[II] Add 0.28 g of N,N-dimethyl-2-phenoxycarbonylsulfonylnicotinamide and 0.14 g of 2-amino-4-chloro-6-methoxypyrimidine prepared according to the process [I] to 8 ml of anhydrous dioxane, and then react the resulting mixture under reflux for about 40 minutes.

After the reaction was completed, the reaction mixture was added to 200 ml of water, and the resulting crystals were filtered off to obtain 0.21 g of N-[(4-chloro-6-methoxypyrimidin-2-yl)aminocarbonyl]-3-dimethylaminocarbonyl- 2-Pyridinesulfonamide, melting point 157-158.5°C.

[Ⅲ] Add 18.3 mg of metallic sodium to 7 ml of anhydrous methanol, and then add 0.11 g of N-[(4-chloro-6-methoxypyrimidin-2-yl) prepared by the procedure [II] thereto Aminocarbonyl]-3-dimethylaminocarbonyl-2-pyridinesulfonamide. The resulting mixture was heated to reflux for 12 hours.

After completion of the reaction, the reaction mixture was added to water and acidified with hydrochloric acid. The precipitated crystals were filtered off, washed with water and dried to obtain 70 mg of the title compound.

The compounds of the present invention represented by the general formula [I] and their salts are shown in Table 3.

The compound of the present invention has herbicidal effect on the following various weeds: sedge weeds (Cyperaceae), such as rice flatsedge (Cyperus iria), Japanese rush (Scirpus juncoides) and Purple nutsedge (Cyperus rotundus), grass Undergraduate weeds (Gramineae) such as barnyard grass (Echinochloacrusgalli), crabgrass (Digitaria adscendens), foxtail grass (Setariaviridis), cricket grass (Eleusine indica), wild oats (Avena fatua), stonegrass sorghum (Sorghum halepense) and goosegrass (Agropyron repens), and broadleaf weeds such as Abutilon theophrasti, tall Ipomoea purpurea, common Chenopodium album, Sida spinosa, horse Portulaca oleracea, Amaranthus viridis, Cassia tora, Solanum nigrum, Polygonum longisetum, Stellaria media, Common cocklebur (Xanthium strumarium) and wavy rice mustard (Cardamine flexuosa). Therefore, the herbicide of the present invention can be applied, for example, in highland farms, and can also be applied to many other occasions, such as agricultural areas (such as orchards) and mulberry fields) and non-agricultural areas (such as forests, agricultural roads, playgrounds, factory areas, and grasslands). The herbicidal composition of the present invention can be used as soil treatment or foliage treatment as needed.

The compounds of the present invention have herbicidal effects particularly on noxious weeds in cereal fields, and thus can be effectively used. The herbicidal compounds according to the invention are applied in the form of granules, wettable powders, emulsifiable concentrates or aqueous solutions. These preparations are prepared by mixing the compound of the present invention with a carrier and various additives such as diluents, solvents, emulsifiers, dispersants or surfactants as required. The active ingredient and one or more agricultural adjuvants are preferably mixed in a weight ratio in the range of 1:99 to 90:10, preferably 5:95 to 60:40. The optimal application rate of the active ingredient cannot be given definitively, because it depends on many factors, such as climatic conditions, weather conditions, soil conditions, agent formulation, weed species to be controlled and the time of application, but the active ingredient The dosage is usually 0.1-100 grams per are (100 square meters), preferably 0.2-50 grams, more preferably 0.5-10 grams.

The herbicidal composition of the present invention can be mixed or used simultaneously with various gaseous agricultural chemicals, fertilizers, soil or safeners. Such use can obtain better effect or function. Other herbicidal compounds which may be mixed with the herbicidal composition of the present invention are listed below. In some cases, synergistic effects can arise.

3,6-dichloro-2-methoxybenzoic acid

2,5-dichloro-3-aminobenzoic acid

(2,4-Dichlorophenoxy)acetic acid

(4-Chloro-2-methylphenoxy)acetic acid

2-Chloro-4,6-bis(ethylamino)-1,3,5-triazine

2-Chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine

2-(4-Chloro-6-ethylamino-1,3,5-triazin-2-ylamino)-2-methylpropionitrile

2-Ethylamino-4-isopropylamino-6-methylthio-1,3,5-triazine

2-Chloro-2′,6′-diethyl-N-(methoxymethyl)-N-acetanilide

2-Chloro-6′-ethyl-N-(2-methoxy-1-methylethyl)-N-acetylo-toluidine

2-Chloro-N-isopropyl-N-acetanilide

2-Chloro-N,N-di-2-propenylacetamide

Dipropylthiocarbamate-S-ethyl ester

Diisobutylthiocarbamate-S-ethyl ester

Dipropylthiocarbamate-S-propyl ester

N-(1-ethylpropyl)-2,6-dinitro-3,4-dimethylaniline

α,α,α-Trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine

2-(3,5-dichlorophenyl)-2-(2,2,2-trichloroethyl)oxirane

3-Isopropyl-(1H)-benzo-2,1,3-thiadiazin-4-one-2,2-dioxide

3-(3,4-Dichlorophenyl)-1-methoxy-1-methylurea

3,5-Dibromo-4-hydroxybenzonitrile

2-Chloro-4-trifluoromethylphenyl-3-ethoxy-4-nitrophenyl ether

For example, N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-3-methylaminocarbonyl (or dimethylaminocarbonyl)-2-pyridinesulfonamide or 6-chloro- (or bromo-, difluoromethyl- or methyl-) N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-3-dimethylaminocarbonyl-2-pyridinesulfonamide Can be used in combination with the following compounds: 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine, 2-(4-chloro-6-ethylamino-1,3, 5-triazin-2-ylamino)-2-methylpropionitrile, 2-chloro-2′,6′-diethyl-N-(methoxymethyl)-N-acetanilide, 2-chloro- 6′-Ethyl-N-(2-methoxy-1-(methylethyl)acetyl-o-toluidine or N-(1-ethylpropyl)-2,6-dinitro-3,4 -Dimethylaniline. The herbicides made by such mixtures are harmless to cereals and can destroy weeds almost completely.

Test example 1

Small pots with an area of 1/1500 are filled with mountain soil and planted with predetermined amounts of seeds of various test plants. When each test plant grows to the predetermined developmental stage [namely: 2.2-3.5 leaf development stage for corn (Zea mays), 2.0-3.5 leaf development stage for wheat (Triticum aestium), 2.0 leaf development stage for common Xanthium -3.5 leaf development stage, 0.5-1.2 leaf development stage for tall plants Asahiba, 0.5-1.2 leaf development stage for Polygonum chinensis, 0.1-1.5 leaf development stage for spiny mallow, 0.1-1.5 leaf development stage for slender Amaranth 0.1-1.5 leaf development stage for plants, 2.0-2.5 leaf development stage for barnyardgrass], an aqueous dispersion was prepared by diluting a solution containing a predetermined amount of each test compound with 5 liters/are of water. Wettable powder, and add 0.2% of a certain dispersant in this aqueous solution. The resulting solution was sprayed on the leaves of the test plants using a small sprayer. 22-37 days after application, the growth degree of the test plants treated above was observed with naked eyes. The evaluation of the weed control effect is divided into 10 grades, wherein 10 means that the test plants are completely killed, and 1 means that there is no effect, as follows Table 4 shows.

Test example 2

In each small pot with an area of 1/10000 ares, mountain soil is respectively loaded, and the seeds of crabgrass crabgrass and black nightshade are planted. Thereafter, when the test plants of crabgrass crabgrass and Solanum nigrum grow to 2 and 0.5 leaf development stages respectively, a certain amount of a kind of medicament to be used is weighed out, so that the contained active ingredient amount is a predetermined amount, and then with 5 liters of water/area. The agent is diluted, 0.2% of an agricultural dispersant is added to the resulting aqueous solution, and the resulting solution is sprayed with a small sprayer. On the 23rd day after spraying, the growth rates of crabgrass and nightshade were visually estimated; the weed control effect was evaluated in the same manner as in Test Example 1. The results are shown in Table 5.

Test example 3

Two 15 centimeters long, germinated rhizomes of sorghum sorghum are planted in small pots with an area of 1/30000 ares, and made to grow in the greenhouse. When sorghum sorghum grows to the 4-5 leaf development stage, A certain amount of a preparation to be used is weighed out to contain a predetermined amount of active ingredient, and then diluted with 5 liters of water/are. In addition, 0.2% of an agricultural dispersant was added to this aqueous solution, and the resulting solution was sprayed on the leaves and stems of Sorghum sorghum plants. 35 days after spraying, the weed control effect on crabgrass was estimated visually. The evaluation method of the weed control effect is the same as that of Test Example 1, and the results are shown in Table 6.

Test example 4

Four germinated tubers of purple nutsedge were planted in small pots with an area of 1/10000 are and allowed to grow in a greenhouse. When the purple njutsedge grows to the 3-4 leaf development stage, weigh out a certain amount of the medicament to be used, so that the amount of the active ingredient is a predetermined amount, and then dilute the medicament with 5 liters of water/are. Further, 0.2% of an agricultural dispersant was added to this aqueous solution, and the resulting solution was sprayed on the leaves of the above-mentioned plants. After 51 days of spraying, the control effect on purple nutsedge was observed with naked eyes. The weed control effect was evaluated in the same manner as in Test Example 1, and the results are shown in Table 7 below.

Formulation examples of the herbicidal composition of the present invention are given below.

Preparation Example 1

parts by weight

(1) Kaolin powder 97

(2) Polyoxyethylene octylphenyl ether 2

(3) Compound No. 15 1

The above ingredients are mixed together and crushed into a powder.

Preparation Example 2

parts by weight

(1) Water-soluble starch 55

(2) Sodium lignosulfonate 5

(3) Compound No. 59 40

The above ingredients are mixed and pulverized to make an aqueous solution.

Preparation Example 3

parts by weight

(1) Kaolin 78

(2) Condensate of sodium naphthalenesulfonate and formaldehyde 2

(3) Polyoxyethylene alkyl allyl sulfate 5

(4) Silica powder 15

Components (1)-(4) were mixed with the compound of the present invention at a mixture ratio of 9:1 to prepare a wettable powder.

Preparation Example 4

parts by weight

(1) Diatomaceous earth 63

(2) Ammonium polyoxyethylene alkylphenyl sulfonate 5

(3) Dialkyl sulfosuccinate

(dialkylsulfosuccinate) 2

(4) Compound No. 29 30

Mix the above ingredients to make wettable powder.

Preparation Example 5

parts by weight

(1) Talc powder 33

(2) Dialkyl sulfosuccinate 3

(3) Polyoxyethylene alkyl sulfate 4

(4) Compound No. 34 60

The above ingredients are mixed together to prepare a wettable powder.

Preparation Example 6

parts by weight

(1) Sodium benzenesulfonate 4

(2) Sodium polycarboxylate (sodium polycarboxylate) 3

(3) Sodium alkylaryl sulfonate 1

(4) Kaolin 12

(4) Compound No. 25 80

The above ingredients are mixed together with water, dried and disintegrated into a wettable powder.

Note: EG is ethylene glycol, Me OH is methanol, Et OH is ethanol, DMF is dimethylformamide, DMSO is dimethyl sulfoxide, Bz is benzyl, -Bu(t) is tert-butyl, and AcOH For acetic acid.

According to the method of route 1 and 2 in the system. Q1 is a hydrogen atom or a halogen atom, NBS is N-bromosuccinimide, and BPO is benzoyl peroxide. The meanings of other abbreviations and symbols are the same as above.

Note: R6 is alkyl or haloalkyl. The meanings of other abbreviations and symbols are the same as above.

Note: The meanings of the abbreviations and symbols are the same as above.

Note: The abbreviations and symbols have the same meaning as above.

Note: The abbreviations and symbols have the same meaning as above.

>

(Table 1, continued from previous page)

11 H 3 HC ₃ H ₇ (iso) 2 152～153

12 ″ ″ CH ₃ CH ₃ ″ 209～211

13 H ″ ″ C ₂ H ₅ ″ 202～203

14 ″ ″ C ₂ H ₅ ″ ″ -

15 5-Cl ″ CH ₃ CH ₃ ″ 155～157

16 6-C ₂ H ₅ ″ ″ ″ ″ 153～154

17 H ″ H CH ₂ CH=CH ₂ ″ 152～153.5

18 ″ ″ ″ CH ₂ CF ₃ ″ 190～196

19 ″ ″ ″ ″ phenyl ″ 186～189

20 4,6 (CH ₃ ) ₂ ″ CH ₃ CH ₃ ″ 199～202

21 6-Br HC ₂ H ₅ ″ -

22 H ″ ″ CH ₂ CH ₂ OCH ₃ ″ 170.5～172.5

23 6-CH ₂ OCH ₃ ″ CH ₃ CH ₃ ″ -

24 5-Cl, 6-OCH ₃ ″ ″ ″ ″ 212～214

25 H ″ ″ H cyclopropyl ″ 180～182

26 ″ ″ ″ CH ₂ C≡CH ″ 203～205

27 ″ ″ -(CH ₂ ) ₄ - ″ 206～209

(Table 1, continued from previous page)

28 6-Cl 3 CH ₃ CH ₃ 2 171～173

29 6-CH ₃ ″ ″ ″ ″ 188.5～190.5

30 6-OCH ₃ ″ ″ ″ ″ -

31 6-C ₂ H ₅ ″ ″ ″ ″ 153～154

32 6-CH ₃ ″ H ″ ″ 230～231.5

33 H ″ -CH ₂ CH ₂ OCH ₂ CH ₂ - ″ 236～238

34 6-N(CH ₃ ) ₂ ″ CH ₃ CH ₃ ″ -

35 6-SCH ₃ ″ ″ ″ ″ 195.5～197

36 6-NHCH ₃ ″ ″ ″ ″ 212～213

37 6-CH ₂ F ″ ″ ″ ″ -

38 6-CH ₂ F ″ ″ ″ ″ -

39 H ″ ″ ″ 2,4-difluoro- ″ ″ 232～237

phenyl

40 ″ ″ h (CH ₂ ) ₃ CH ₃ ″ -

41 6-CH ₂ OCH ₂ CF ₃ ″ CH ₃ CH ₃ ″ 2

42 H 4 H H ″ 3 239～241

43 ″ 2 CH ₃ ″ ″ -

44 6-OCH ₂ CF ₃ 3 ″ ″ 2 -

(Table 1, continued from previous page)

45 6-Br 3 CH ₃ CH ₃ 2 154～156

46 6-OCH ₂ CH ₃ 4 ″ ″ ″ -

47 H ″ ″ ″ ″ ″ ″ -

48 ″ 2 ″ ″ ″ 3 169～170

49 6-C ₃ H ₇ (iso) 3 ″ ″ 2 -

50 5-CHF ₂ ″ ″ ″ ″ -

51 6-CF ₃ ″ ″ ″ ″ 151～153

52 ″ ″ ″ C ₂ H ₅ ″ -

53 ″ ″ ″ H CH ₃ ″ -

54 6-CH ₃ ″ CH ₃ C ₂ H ₅ ″ -

55 6-Br ″ H CH ₃ ″ -

56 6-Cl ″ ″ ″ ″ ″ ″ -

57 6-CHF ₂ ″ ″ ″ ″ -

(Table 3, continued from previous page)

8 H 3 CH ₃ CH ₂ CF ₃ 2 OCH ₃ OCH ₃ 171.5～173.5

9 5-Cl ″ ″ CH ₃ ″ ″ ″ 152～155

10 H ″ ″ H phenyl ″ ″ ″ ″ 188～190

11 4,6-(CH ₃ ) ₂ ″ CH ₃ ″ ″ ″ 201～204

12 5-Cl, 6-OCH ₃ ″ ″ ″ ″ ″ ″ 166～168

13 H ″ H CH ₂ C≡CH ″ ″ ″ 154.5～157

14 ″ ″ - (CH ₂ ) ₄ - ″ ″ ″ 158～162

15 6-Cl ″ CH ₃ CH ₃ ″ ″ ″ 183～186

16 H ″ ″ COOCH ₃ ″ ″ ″ 162～164

17 6-OC ₂ H ₅ ″ ″ CH ₃ ″ ″ ″ 208～209

18 6-C ₂ H ₅ ″ ″ ″ ″ ″ ″ 193～194.5

19 6-CH ₂ OCH ₃ ″ ″ ″ ″ ″ ″ 183～185

20 4,6-(CH ₃ ) ₂ ″ H ″ ″ ″ ″ 179～181

21 6-F ″ CH ₃ ″ ″ ″ ″ 115～124

22 6-Br ″ HC ₂ H ₅ ″ ″ ″ -

23 6-CH ₃ ″ CH ₃ C ₃ H ₇ (Positive) ″ ″ ″ -

24 6-Cl ″ ″ CH ₃ ″ CH ₃ ″ -

(Table 3, continued from previous page)

25 H 3 H CH ₃ 2 OCH ₃ OCH ₃ 147～149.5

26 ″ ″ ″ C ₂ H ₅ ″ ″ ″ 163～168

27 ″ ″ ″ C ₃ H ₇ (different) ″ ″ ″ 166.5～168.5

28 6-C ₂ H ₅ ″ ″ CH ₃ ″ ″ ″ -

29 H ″ CH ₃ ″ ″ ″ ″ 169～173

30 6-C ₃ H ₇ (different) ″ ″ ″ ″ ″ ″ ″ -

31 6-I ″ ″ ″ ″ ″ ″ ″ ″ ″ ″ -

32 H ″ C ₂ H ₅ ″ CH ₃ ″ -

33 ″ ″ CH ₃ ″ OCH ₃ ″ 170.5～172

34 6-CH ₃ ″ ″ CH ₃ ″ ″ ″ 170～174

35 6-OCH ₃ ″ ″ ″ ″ 206～207.5

36 5-CHF ₂ ″ ″ ″ ″ ″ ″ ″ -

37 H ″ C ₂ H ₅ C ₂ H ₅ ″ ″ ″ 109～111

38 6-CH ₃ ″ H CH ₃ ″ ″ ″ 183～185

39 6-CF ₃ ″ CH ₃ ″ ″ ″ ″ 189～191

40 6-Br ″ ″ C ₂ H ₅ ″ ″ ″ -

41 6-N(CH ₃ ) ₂ ″ ″ CH ₃ ″ ″ ″ 199～201.5

(Table 3, continued from previous page)

42 6-SCH ₃ 3 CH ₃ CH ₃ 2 OCH ₃ OCH ₃ 200～201.5

43 H ″ ″ ″ ″ CH ₃ ″ 177～185

44 6-NHCH ₃ ″ ″ ″ ″ OCH ₃ ″ 183～185

45 6-Br ″ ″ ″ ″ ″ ″ ″ ″ ″ 201.5～203.5

111～114

46 H ″ ″ ″ ″ ″ OC ₂ H ₅ (decomposition)

47 ″ ″ H (CH ₂ ) ₃ CH ₃ ″ ″ OCH ₃ 156～158

48 6-CH ₂ F ″ CH ₃ CH ₃ ″ ″ ″ 180～181

49 6-CHF ₂ ″ ″ ″ ″ ″ ″ 194～195

50 H ″ ″ 2,4-two″ ″ ″ ″ 156～158

Fluorophenyl

51 ″ ″ ″ ″ ″ 4-chloro″ ″ ″ ″ 241～243

Phenyl

52 N-oxide pyridine analogue of compound No. 29 169.5～171

53 6-CF ₃ 3 CH ₃ C ₂ H ₅ 2 OCH ₃ OCH ₃ -

54 6- ″ ″ CH ₃ ″ ″ ″ 179～180

CH ₂ OCH ₂ CF ₃

55 H 2 ″ ″ ″ 3 ″ ″ ″ 196～198

56 ″ 4 H ″ ″ ″ ″ ″ ″ 129～132

57 ″ 2 ″ ″ ″ ″ ″ ″ ″ 122～125

58 6-OCH ₂ CF ₃ 3 CH ₃ ″ 2 ″ ″ 186.5～189

(Table 3, continued from previous page)

195～215

59 Sodium salt of compound No. 29 (decomposition)

60 Monomethylamine salt of compound No. 29 125～128

61 N-oxide pyridine analogue of compound No. 34 163～164.5

62 Potassium salt of compound No. 25 -

63 6-I 3 H CH ₃ 2 OCH ₃ OCH ₃ -

64 6-CF ₃ ″ ″ ″ ″ ″ ″ -

65 6-CH ₃ ″ CH ₃ C ₂ H ₅ ″ ″ ″ -

66 6-Br ″ H CH ₃ ″ ″ ″ -

67 6-Cl ″ ″ ″ ″ ″ ″ ″ ″ ″ -

68 6-CHF ₂ ″ ″ ″ ″ ″ ″ ″ -

69 Sodium salt of compound No. 15

70 Sodium salt of compound No. 25

71 Sodium salt of compound No. 34

72 Sodium salt of compound No. 45

73 Sodium salt of compound No. 49

74 Dimethylamine salt of No. 34 compound

table 5

Compound No. Active Ingredient Dosage Weed Control Grade

(g/are) Crabgrass Solanum nigrum

5.0 8 10

25

2.5 7 10

5.0 10 10

29

2.5 10 10

Table 6

Compound No. Active Ingredient Dosage Weed Control Grade

(g/are)

5.0 9

2.5 2.5 8～9

1.25 7

0.625 4

2.5 9～10

29 1.25 9～10

0.625 8～9

0.313 7

2.5 9

34 1.25 9

0.625 8

0.313 6～7

Table 7

Compound No. Active Ingredient Dosage Weed Control Grade

(g/are)

5.0 10

15 2.5 10

1.25 10

0.625 10

5.0 10

21 2.5 10

1.25 9

0.625 8

2.5 10

29 1.25 10

0.625 10

0.313 8

5.0 10

34 2.5 10

1.25 10

0.625 9

Claims (5)

1. A herbicidal composition comprising a herbicidally effective amount of a substituted pyridinesulfonamide compound of the following formula or a salt thereof and agricultural adjuvants. 2. The herbicidal composition as claimed in claim 1, wherein said compound or its salt is mixed with an agricultural adjuvant in a ratio of 1:99 to 90:10. 3. The herbicidal composition as claimed in claim 1, wherein said compound is N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-3-dimethylaminocarbonyl-2-pyridine-sulfonamide . 4. The herbicidal composition as claimed in claim 1, wherein said compound is N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-3-dimethylaminocarbonyl-2-pyridine-sulfonamide sodium salt. 5. A method for killing harmful weeds in farmland with the herbicidal composition claimed in claim 1, wherein the composition contains a herbicidally effective amount of a substituted pyridinesulfonamide compound of the following formula or

Its salt and agricultural auxiliaries, the amount of the compound is 6.1-100 g/are.