HRP920312A2 - New method of combatting insect eggs and ovicidal compositions - Google Patents

Description

Field of invention

This invention relates to new substituted pyridinesulfonamide compounds and their salts, herbicidal preparations containing them as active substances, and to a process for the production of these compounds.

Description of previous knowledge

The substituted pyridinesulfonamide compound of this invention is distinguished by the fact that the pyridine ring has an N-substituted aminocarbonyl group. Such a substituted pyridinesulfonamide compound is known by the general formulas in U.S.P. But. 4,518,776, European patent application no. 101,670 and U.S.P. But. 4,521,597. However, the substituted pyridinesulfonamide of the present invention is not specifically described in the above prior patents. Some substituted pyridinesulfonamide compounds are described in U.S.P. But. 4,435,206. However, in this compound the pyridine ring is not N-substituted with an aminocarbonyl group. A large number of herbicide analogues have been developed that contain a sulfonamide compound as an active substance. However, so far no herbicides have been found that show high safety against cereals, and that have a high herbicidal effect.

Summary of the invention

Here, the inventors have made extensive research regarding the relationship between chemical structure and physiological activity against plants for sulfonamide compounds. Separately, these inventors did further research to find herbicides for cereals. As a result, these inventors have come to the conclusion that a pyridinesulfonamide compound with a pyridine ring having an N-substituted aminocarbonyl group, and especially a substituted group (if any) and a sulfonamide nucleus substituted on the nitrogen atom with a specifically substituted pyrimidin-2-ylaminocarbonyl group is an effective herbicide. in the grain fields, and that's how the inventors came up with this invention.

This invention provides a substituted pyridinesulfonamide compound, its salts, a herbicidal composition containing them, and a process for their preparation. Substituted pyridinesulfonamide compounds are represented by the following general formula:

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group, wherein each of R1 and R2 independently represents a hydrogen atom, an alkyl group, a haloalkyl group, an alkenyl group, an alkynyl group, an alkoxyl group, a haloalkyl group, an alkoxyalkyl group, a haloalkoxyalkyl group, a cycloalkyl group, a halocycloalkyl group, an alkyloxycarbonyl group, a haloalkoxycarbonyl group, a phenyl group or a halophenyl group, with the proviso that when one of R1 and R2 represents a hydrogen atom, the other represents one of the groups other than a hydrogen atom; R1 and R2 together with the adjacent nitrogen atom can form a heterocyclic ring; Y represents a halogen atom, an alkyl group, a haloalkyl group, an alkyl group, a haloalkyl group, an alkylthio group, a haloalkylthio group, an alkoxyalkyl group,

[image] hydrogen atom or alkyl group); n is 0, or an integer of 1 or 2; and each of X1 and X2 independently represents a methyl group, a methoxyl group, or an ethoxyl group.

Salts of the substituted pyridinesulfonamide compounds of this invention include alkali metal salts (for example, sodium and potassium), alkaline earth metal salts (for example, magnesium and calcium), and amine salts (for example, monomethylamine, dimethylamine, and triethylamine). These salts can be prepared by usual procedures.

A detailed description of the desired performance

In the general formula (I), the haloalkyl, haloalkyl, haloalkoxyalkyl, haloalkoxycarbonyl, halocycloalkyl or halophenyl groups represented by R1 and R2, and the haloalkyl, haloalkyl, haloalkylthio or haloalkylthio groups represented by Y may be substituted with one or more halogen atoms.

The alkyl group or ring represented by R1, R2, R3, R4 and Y in the general formula (I) is a group or ring having 1 to 6 carbon atoms, and examples of such groups are methyl group, ethyl group, propyl group, and butyl group. . The alkenyl group or ring represented by R1 and R2 has 2 to 6 carbon atoms, and examples of such groups are propenyl and butenyl. An alkynyl group or ring has 2 to 6 carbon atoms, and examples of such groups are propynyl and butynyl. A cycloalkyl group has 3 to 6 carbon atoms, and examples of such a group are a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples of halogen atoms in R1, R2 and Y are fluorine, chlorine, bromine and iodine. R1 and R2 together with a nitrogen atom can form a heterocyclic ring. Examples of heterocyclic rings are morpholine ring, ethyleneimine ring, pyrrolidine ring and piperidine ring.

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

[image]

More preferred embodiments will be 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, an alkyl group, a haloalkyl, an alkoxy group, or an alkoxyalkyl group, and preferably a chlorine atom, a bromine atom, a methyl group, or a difluoromethyl group, each of which is attached to the 6-position of the pyridine ring; n is 0, 1 or 2, preferably 0 or 1.

(3) Each of X1 and X2 independently represents a methoxyl group.

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

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.

Substituted pyridinesulfonamide compounds represented by the general formula (I) and their salts according to this invention can be obtained by the following procedures:

The pyridine compound represented by the general formula (II)

R-SO2Z1 (II)

wherein R represents as defined above and Z1 represents an NH2 group, -NCO group, -NHCOCl group, or -NHCOOR5 group (where R5 represents an alkyl or aryl group) is reacted with a pyrimidine compound represented by the following general formula:

[image]

wherein each of X3 and X4 independently represents a halogen atom, a methyl group, a methoxyl group, or an ethoxyl group, Z2 represents an NH2 group, -NCO group, -NHCOCl group, or -NHCOOR5 group (wherein R5 is as defined above), with provided that when Z1 represents an NH2 group, Z2 represents an -NCO group, a NHCOCl group, or a -NHCOOR5 group, and that when Z2 represents an NH2 group, Z1 represents an -NCO group, a -NHCOCl group, or a -NHCOOR5 group. Then, if X3 and/or X4 represents a halogen atom, methoxylation or ethoxylation is performed. In addition, if desired, it is treated for the formation of salt.

More specifically, the pyridinesulfonamide compound and its derivative can be prepared by methods /A/ to /G/.

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The following method can also be used:

[H] R-SO2NHCONH2 + (III-4) 130 ~ 250°C (I)

(II-6) 0.5 ~ 24h

In the reaction equations of methods /A/ to /H/, Hal denotes a halogen atom and R, R5, X, X2 and X3 are the same as described above. The compound represented by the general formula (II-5) can be prepared according to the sequence 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) can be a phenyl or naphthyl group which can be substituted with one or more chlorine atoms or with one or more methyl groups. In methods /A/ and /D/, 1,8-diazabicyclo/5.4.0/-7-undecene can be added to speed up the reactions, if desired. In methods /B/, /C/, /E/ and /F/ 1,4-diazabicyclo/2.2.2/-octane can be added, if desired. In methods /B/, /C/, /E/ and /F/ it is possible, if desired, to add an alkali such as triethylamine or pyridine. Methods /A/ to /H/ are carried out in the presence of a solvent, if desired. Examples of solvents are: aromatic hydrocarbons (for example benzene, toluene, xylene and chlorobenzene); cyclic or acyclic aliphatic hydrocarbons (for example chloroform, carbon tetrachloride, methylene chloride, dichloroethane, trichloroethane, hexane and cyclohexane); ethers (for example, diethyl ether, dioxane and tetrahydrofuran); nitriles (for example acetonitrile, propionitrile, or acrylonitrile); and aprotic polar solvents (for example dimethyl sulfoxide and sulfolane).

(1) It has been shown that the pyridine compound (II-1') in the general formula (II-1) as a starting substance for the reaction formula can be obtained by the process via methods 1 and 2:

[image]

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Note: EG is ethylene glycol, MeOH is methanol, EtOH is ethanol, DMF is dimethylformamide, DMSO is dimethylsulfoxide, BZ is a benzyl group, Bu(t) is a tertiary butyl group, and AcOH is acetic acid.

(2) It has been shown that, if Y in the general formula (II-1') is an alkyl group substituted with one or more fluorine atoms, the product can also be prepared by the process shown as method 3 below.

[image]

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according to the procedures shown in methods 1 and 2.

Q1 is a hydrogen atom or a halogen atom, NBS is N-bromosuccinimide, and BPO is benzoyl peroxide. Other abbreviations and symbols have the same meanings as described above.

(1) It has been shown that, if Y in the general formula (II-1') is an alkyl, haloalkyl, alkylthio or haloalkylthio group, the product can also be obtained by the method according to method 4 below.

[image]

formula (continued)

Note: R6 is alkyl or haloalkyl. Other abbreviations and symbols have the same meanings as described above.

(2) It was shown that if Y in the general formula (II-1') is an alkyloxymethyl or haloalkyloxymethyl group, the product can also be obtained by the method shown below in method 5.

[image]

Note: Abbreviations and labels have the same meanings as described above.

[image] can also be obtained by following the method shown below 6.

[image]

Note: Abbreviations and labels have the same meanings as described above.

(6) It was shown that if Y in the general formula (II-1') represents a halogen atom, the product can also be obtained by the method shown below in method 7.

[image]

Note: Abbreviations and labels have the same meanings as described above.

(7) It has been shown that the 3-pyridinesulfonamide compound represented by the general formula (II-1') can also be obtained by the method 8 shown below.

[image]

Note: Abbreviations and labels have the same meanings as described above.

(8) It has been shown that the compound pyridine-N-oxide represented by the general formula (II-1') can also be obtained by the method 9 shown below.

[image]

(9) It has been shown that the compounds represented by the general formulas (II-2) to (II-4) can be obtained from the compounds represented by the general formula (II-1) by the method 10 shown below.

[image]

The reaction conditions for obtaining the starting compound, such as the reaction temperature, reaction time, solvent used if necessary, alkaline substance, etc., can conveniently be selected from those commonly used in analogous reactions.

Examples of the synthesis of intermediates according to this invention will be described below:

Synthesis of intermediates,

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 the reaction was carried out under reflux for 2 hours. After completion of the reaction, excess thionyl chloride was distilled and removed, and 30 ml of methylene chloride was added to the mixture, and then 2.77 g of dimethylamine hydrochloride salt was added. 8.60 g of triethylamine was added dropwise over one hour, and the resulting mixture was allowed to react at room temperature for about one hour.

After completion of the reaction, the reaction product was poured into water for extraction with methylene chloride. The methylene chloride layer was dried with anhydrous sodium sulfate, and the methylene chloride was distilled under reduced pressure. The obtained residue was purified by chromatography on a silica gel column, whereby 5.5 g of 2,5-dichloro-N,N-dimethylnicotinamide with a melting point of 120-122°C was obtained.

/II/ A mixture of 3.0 g of 2,5-dichloro-N,N-dimethylnicotinamide obtained by process /I/, 1.70 g of benzyl mercaptan, and 5 ml of dimethyl sulfoxide was added dropwise to a suspension of 1.8 g of anhydrous potassium carbonate. in 28 ml of dimethylsulfoxide at 80°C for about one hour. The resulting mixture was reacted at 130 to 140°C for 30 minutes.

After the finished reaction, the reaction product was poured into water for extraction with methylene chloride. The methylene chloride layer was dried with anhydrous sodium sulfate, and the methylene chloride was distilled off under reduced pressure. The resulting residue was purified by chromatography on a silica gel column to obtain 2.18 g of oily 2-benzylthio-5-chloro-N,N-dimethylnicotinamide.

/III/ Chlorine gas was introduced into 20 ml of 50% acetic acid solution containing 2.36 g of 2-benzylthio-5-chloro-N,N-dimethylnicotinamide at 0 to 5°C. The reaction was stopped when an excess of chlorine appeared.

After the end of the reaction, the reaction product was poured into 150 g of ice and 200 ml of methylene chloride in order to separate the methylene chloride layer. The layer was washed with 300 ml of ice and water to cool to 0°C. Tert-butylamine was then added dropwise and the mixture was stirred until the temperature of this layer reached room temperature. The reaction solution was adjusted to weakly alkaline and the reaction was terminated.

After completion of the reaction, the reaction product was poured into water for extraction with methylene chloride. The extracted methylene chloride was washed with anhydrous sodium sulfate, and the methylene chloride was distilled. The obtained residue was purified by chromatography on a silica gel column so that 1.21 g of 2-tert.-butylaminesulfonyl-5-chloro-N,N-dimethylnicotinamide with a melting point of 143 to 145°C was obtained.

/IV/ 1.0 g of 2-tert.-butylaminesulfonyl-5-chloro-N,N-dimethylnicotinamide obtained by process /III/ was added to 10 ml of trifluoroacetic acid and the reaction was carried out under reflux for one hour.

After completion of the reaction, trifluoroacetic acid was distilled from the reaction product under reduced pressure. The residue was then purified by chromatography on a silica gel column, whereby 0.71 g of 2-aminosulfonyl-5-chloro-N,N-dimethylnicotinamide with a melting point of 155 to 157°C was obtained.

Synthesis of intermediates,

Example 2

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

/I/ Mixture of 7.0 g of 2,6-dichloro-N,N-dimethylnicotinamide (m.p. 62.5 to 65°C) obtained from 2,6-dichloronicotinic acid following the same procedure as in procedure /I/ of the synthesis of intermediates from Example 1, 3.8 g of benzyl alcohol and 20 ml of dimethylsulfoxide, was added dropwise to a suspension of 6.6 g of anhydrous potassium carbonate in 50 ml of dimethylsulfoxide at 130° to 140°C for about one hour, and the resulting mixture was reacted at 150° C for about two hours.

After completion of the reaction, the reaction product was poured into water for extraction with methylene chloride. The methylene chloride layer was dried with anhydrous sodium sulfate, and the methylene chloride was distilled under reduced pressure. The resulting residue was purified by chromatography on a silica gel column, whereby 6.0 g of oily 6-benzoyloxy-2-chloro-N,N-dimethylnicotinamide was obtained.

/II/ 0.69 g of 6-benzoyl-2-benzylthio-N,N-dimethylnicotinamide (oily product) obtained by using 6-benzoyloxy-2-chloro-N,N-dimethylnicotinamide following the same procedure as described in procedure /II / synthesis of intermediates from Example 1, was mixed with 6 ml of concentrated hydrochloric acid, and the resulting mixture was reacted with stirring at room temperature for about 15 hours.

After completion of the reaction, the reaction solution was poured into water to extract the desired product with methylene chloride. The methylene chloride layer was dried with anhydrous sodium sulfate, and the methylene chloride was distilled under reduced pressure. The obtained residue was purified by chromatography on a silica gel column, which yielded 0.41 g of 2-benzylthio-N,N-dimethyl-6-hydroxynicotinamide, which has a melting point of 52 to 60°C.

/III/ 1.0 g of 2-benzylthio-N,N-dimethyl-6-hydroxynicotinamide obtained in the previous procedure /II/ and 0.3 ml of dimethylformamide were poured into 5 ml of thionyl chloride, and the resulting mixture was reacted under reflux for about one hour.

After the completion of the reaction, the reaction product was poured into water for extraction of the desired product with methylene chloride. The methylene chloride layer was washed with water and dried with anhydrous sodium sulfate. Methylene chloride was then distilled under reduced pressure, and the obtained residue was purified by chromatography on a silica gel column, whereby 0.45 g of oily 2-benzylthio-6-chloro-N,N-dimethylnicotinamide was obtained.

/IV/ Using the above product and following the same procedure as in procedures /III/ and /IV/ from Example 1, 2-aminosulfonyl-6-chloro-N,N-dimethylnicotinamide with a melting point of 171 to 173°C was obtained.

Synthesis of intermediates,

Example 3

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

/I/ 0.231 g of sodium metal was added to 50 ml of anhydrous ethanol to prepare an ethanolic solution of sodium ethoxide. 2.0 g of 2,6-dichloro-N,N-dimethylnicotinamide obtained following the same procedure as in procedure /I/ for the synthesis of intermediates from Example 1, was added to the solution and the mixture was reacted under reflux conditions for about one hour. The reaction solution was poured into water for extraction with methylene chloride. The methylene chloride layer was washed with water and dried with anhydrous sodium sulfate. Methylene chloride was then distilled under reduced pressure, and the obtained residue was purified by chromatography on a silica gel column, whereby 1.95 g of 2-chloro-N,N-dimethyl-6-ethoxynicotinamide was obtained.

/II/ By using the above product and following the same procedure as in procedures /II/, /III/ and /IV/ of the synthesis of intermediate products from Example 1, 2-aminosulfonyl-N,N-dimethyl-6-ethoxynicotinamide with a melting point of 150 .5 to 151.5°C.

Synthesis of intermediates,

Example 4

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

/I/ 0.302 g of 2-tert.-butylaminosulfonyl-6-chloro-N,N-dimethylnicotinamide was added to 10 ml of dimethyl sulfoxide solution containing 0.116 g of sublimation dried potassium fluoride, and the resulting mixture was reacted with stirring at 150°C. for about 3 hours.

After completion of the reaction, the reaction solution was poured into 100 ml of water for extraction with methylene chloride. The extracted substance was washed several times with water and dried with anhydrous sodium sulfate. Methylene chloride was then distilled under reduced pressure, and the residue was purified by chromatography on a silica gel column so that 0.204 g of 2-tert.-butylaminosulfonyl-N,N-dimethyl-6-fluoronicotinamide was obtained.

/II/ By using the product and following the same procedures as in stage /IV/ of the synthesis of intermediates from Example 1, 2-aminosulfonyl-N,N-dimethyl-6-fluoronicotinamide with a melting point of 164 to 165°C was obtained.

Synthesis of intermediates,

Example 5

Synthesis of 2-aminosulfonyl-N-methylnicotinamide

/I/ 250 ml of dry methanol was saturated with hydrogen chloride gas, and 250 ml of methanol and 30 g of 2-mercaptonicicotinic acid were added. The resulting solution was reacted overnight at room temperature.

After the completion of the reaction, the reaction solution was transferred to weakly alkaline with gaseous ammonia, and methanol was distilled under reduced pressure. Then the obtained crystalline substance was washed with water and filtered. The filtered crystals were dried under reduced pressure so that 24 g of methyl-2-mercaptonicotinate was obtained, which has a melting point of 136 to 140°C.

/II/ 10 g of methyl-2-mercaptonicotinate obtained by procedure /I/ was added to the suspension prepared by diluting 50 ml of acetic acid with 50 ml of water. Chlorine gas was introduced into the reaction system at a temperature of 0°C, or below, and the reaction was terminated when excess chlorine appeared.

After completion of the reaction, the resulting solution was added to a mixture of 150 g of ice and 500 ml of methylene chloride in order to separate the methylene chloride layer. The layer was washed with 500 ml of ice and water and cooled to 0°C. Then 12.9 g of tert-butylamine was added dropwise to the above solution and stirred until the resulting solution reached room temperature. After stirring, the reaction solution was added to 500 ml of water and extracted with methylene chloride. After drying with sodium sulfate, methylene chloride was distilled so that 13 g of crude crystals were obtained. The crystals were recrystallized with methylene chloride and n-hexane so that methyl-2-tert.-butylaminosulfonylnicotinate was obtained, which has a melting point of 169 to 171°C.

/III/ 1.0 g of this product was added to 20 ml of anhydrous methanol, the excess methylamine was absorbed, and it was stirred for 15 hours.

After completion of the reaction, the reaction product was poured into water for extraction with methylene chloride. After extraction, the layer was dried with anhydrous sodium sulfate and methylene chloride was distilled under reduced pressure. Thus, 0.73 g of 2-tert.-butylaminosulfonyl-N-methylnicotinamide, which has a melting point of 189 to 192°, was obtained.

/IV/ By using the product and following the same procedure as in stage /IV/ of the synthesis, intermediate products from Example 1, 2-aminosulfonyl-N-methylnicotinamide was obtained, which has a melting point of 207 to 209.5°C.

Synthesis of intermediates,

Example 6

Synthesis of 2-aminosulfonyl-N,N-dimethylnicotinamide

/Mode A/

/I/ Under a nitrogen atmosphere, at 10°C or lower, 10 ml of n-hexane containing 19% trimethylaluminum was added to a solution prepared by dissolving 1.3 ml of dimethylamine in 10 ml of anhydrous benzene. The resulting mixture was reacted until its temperature reached room temperature. A solution prepared by dissolving methyl-o-2-tert.-butylaminosulfonylnicotinate in 40 ml of benzene and 20 ml of methylene chloride was added to the reaction solution. The resulting mixture was then stirred under reflux conditions for about 9 hours.

After completion of the reaction, the reaction solution was poured into dilute hydrochloric acid for extraction with methylene chloride. The extracted substance was dried with anhydrous sodium sulfate, methylene chloride was distilled under reduced pressure, and the residue was purified by chromatography on a silica gel column so that 1.0 g of 2-tert.-butylaminosulfonyl-N,N-dimethylnicotinamide was obtained.

/II/ By using the above product and following the same procedure as in stage /IV/ of the synthesis of intermediates from Example 1, 2-aminosulfonyl-N,N-dimethylnicotinamide was obtained, which has a melting point of 209 to 211°C.

/Mode B/

Chlorine gas was introduced into 50 ml of 50% acetic acid solution and 2.7 g of 2-benzylthio-N,N-dimethylnicotinamide until excess chlorine appeared.

After completion of the reaction, the reaction mixture was added to 200 ml of ice and water for extraction with 60 ml of methylene chloride. The methylene chloride layer was then washed with 100 ml of ice and water and cooled to 0°C. Gaseous ammonia was introduced into the solution until the solution became alkaline. After the methylene chloride was distilled, 15 ml of water was added to the residue, and the resulting mixture was stirred. The resulting crystals were filtered and washed with a small amount of water. The crystals were then dried under reduced pressure to obtain 1.27 g of 2-aminosulfonyl-N,N-dimethylnicotinamide, which has a melting point of 209 to 211°C.

Synthesis of intermediates,

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 under reflux conditions for 4 hours. After the excess thionyl chloride was distilled from the reaction solution under reduced pressure, 500 ml of methylene chloride was added, and gaseous methylamine was introduced at room temperature until the solution became slightly basic. The resulting methylamine hydrochloride was filtered and the filtrate was concentrated. The precipitated crystals were recrystallized from n-hexane and methylene chloride to obtain 27 g of 2-chloro-N-methylnicotinamide, which has a melting point of 106 to 107°C.

/II/ 10 ml of dimethylformamide containing 5 g of 2-chloro-N-methylnicotinamide, prepared by the same procedure as in step /I/ of this example, was added dropwise at 0 to 5°C to the suspension obtained by adding 1.17 g of 60% sodium -hydride in 50 ml of dimethylformamide. The resulting mixture was reacted at 0 to 5°C for about 30 minutes, and 3.5 g of ethyl bromide was added dropwise at 0°C. The resulting solution was reacted at room temperature for 2.5 hours, and the reaction solution was poured into water for extraction with methylene chloride. The extracted substance was washed with water and dried with anhydrous sodium sulfate. Methylene chloride was then distilled under reduced pressure, and the residue was purified by chromatography on a silica gel column, so that 5.7 g of oily 2-chloro-N-ethyl-N-methylnicotinamide was obtained.

/III/ By using this product and following the same procedure as in stages /II/ to /IV/ of the synthesis of intermediates from Example 1, 2-aminosulfonyl-N-ethyl-N-methylnicotinamide was obtained, which has a melting point of 202 to 203°C.

Synthesis of intermediates,

Example 8

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

/I/ One 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 reacted under reflux conditions for about 2 hours. Excess thionyl chloride was distilled off under reduced pressure, and 50 ml of methylene chloride was added to the residue. The resulting mixture was added dropwise to a mixture of 30 ml of a 30% aqueous solution of dimethylamine and 50 ml of methylene chloride, and the resulting solution was reacted at room temperature for 15 minutes.

After completion of the reaction, the reaction mixture was poured into water for extraction with methylene chloride. The methylene chloride layer was washed with water and dried with anhydrous sodium sulfate. Methylene chloride was distilled under reduced pressure and the residue was purified by chromatography on a silica gel column to obtain 1.57 g of 2-chloro-3-N,N-dimethylaminocarbonyl-6-methylpyridine (m.p. 66-67°C).

/II/ By using this product and following the same procedure as in stages /II/ to /IV/ for the synthesis of intermediates from Example 1, 2-aminosulfonyl-N,N-dimethyl-6-methylnicotinamide was obtained, which has a melting point of 188.5 up to 190.5°C.

Synthesis of intermediates,

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 conditions for about 3 hours.

After completion of the reaction, excess thionyl chloride was distilled off under reduced pressure, and 500 ml of methylene chloride was added. Anhydrous methanol was added to the mixture at a temperature between room temperature and 40°C. After adding dropwise, the resulting mixture was reacted under reflux conditions for about one hour.

After completion of the reaction, the reaction solution was added to 500 ml of water and stirred with methylene chloride. After the residue was washed with water and dried with anhydrous sodium sulfate, methylene chloride was distilled under reduced pressure. The residue was purified by chromatography on a silica gel column so that 27 g of methyl-2,6-dichloronicotinate was obtained, which has a melting point of 45.5 to 48.0°C.

/II/ Using this product and following the same procedure as in the step of synthesis of intermediates from Example 3, /II/ synthesis of intermediates from Example 1 (Method A), /I/ synthesis of intermediates from Example 6 and /III/ to /IV/ synthesis of intermediates from Example 1, 2-aminosulfonyl-N,N-dimethyl-6-methoxynicotinamide was obtained.

Synthesis of intermediates,

Example 10

Synthesis of 2-aminosulfonyl-6-difluoromethyl-N,N-dimethyl-nicotinamide

/I/ A mixture of 11.5 g of methyl-2-tert.-butylaminosulfonyl-6-nicotinate obtained following the same procedure as in steps /I/ and /II/ of the synthesis of intermediates from Example 5, 186 ml of carbon tetrachloride, 14.84 g of N -bromosuccinimide, and 0.68 g of benzoyl peroxide, was heated at reflux for three hours.

After completion of the reaction, the reaction mixture was filtered, and the filtrate was condensed and purified by chromatography on a silica gel column so that 4.5 g of methyl-2-tert.butylaminosulfonyl-6-dibromomethylnicotinate was obtained.

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

After completion of the reaction, the reaction mixture was added to water for extraction with methylene chloride. The extracted substance was washed with water and dried over anhydrous sodium sulfate, and the solvent was distilled. The residue was purified by chromatography on a silica gel column to obtain 2.92 g of methyl 2-tert.-butylaminosulfonyl-6-formylnicotinate.

/III/ 5 ml of methylene chloride solution and 0.62 g of sulfur diethylaminotrifluoride were added to 19 ml of methylene chloride solution of 0.48 g of methyl 2-tert.-butylaminosulfonyl-6-formylnicotinate, and the mixture was stirred for one hour at room temperature.

After completion of the reaction, the reaction mixture was added to water, extracted with methylene chloride, washed with water, and dried with anhydrous sodium sulfate. After that, the solvent was distilled. The residue was purified by chromatography on a silica gel column so that 0.25 g of methyl-2-tert.-butylaminosulfonyl-6-difluoromethylnicotinate was obtained.

/IV/ A mixture of 0.50 g of the above product and 10 ml of anhydrous methanol saturated with dimethylamine was left overnight at room temperature.

After completion of the reaction, the solvent was distilled from the reaction mixture, and the residue was purified by chromatography on a silica gel column so that 0.15 g of 2-tert.butylaminosulfonyl-6-difluoromethyl-N,N-dimethylnicotinamide was obtained.

/V/ By using the above product and following the same procedure as in stage /IV/ of the synthesis of intermediates from Example 1, 2-aminosulfonyl-6-difluoromethyl-N,N-dimethylnicotinamide was obtained.

Synthesis of intermediates,

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. Gaseous hydrogen bromide was introduced into this mixture for 30 minutes and the mixture reacted for another 30 minutes.

After completion of the reaction, the reaction mixture was cooled and added to ice water, extracted with methylene chloride, washed with sodium bicarbonate solution, then with water, and dried with anhydrous sodium sulfate. Methylene chloride was distilled and the residue was purified by silica gel column chromatography to give 1.0 g of 2-benzylthio-6-bromo-N,N-dimethylnicotinamide, which has a melting point of 105 to 106°C.

/II/ By using this product and following the same procedure as in stages /III/ and /IV/ of the synthesis of intermediate products from Example 1, 2-aminosulfonyl-6-bromo-N,N-dimethylnicotinamide was obtained, which has a melting point of 154 to 156° C.

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

Table 1

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[image] [image]

Examples of the synthesis of compounds according to the invention will be described below.

Example of synthesis no. 1

Synthesis of 5-chloro-N-/(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl/-3-dimethylaminocarbonyl-2-pyrimidinesulfonamide

(connection no. 9)

0.19 g of 1,8-diazabicyclo/5.4.0/-7-undecene was added to a suspension prepared by adding 0.30 g of 2-aminosulfonyl-5-chloro-N,N-dimethylnicotinamide and 0.35 g of 2-phenoxycarbonylamino- of 4,6-dimethoxypyrimidine in 10 ml of anhydrous acetonitrile, and the resulting mixture was reacted at room temperature for 45 minutes.

After completion of the reaction, the reaction mixture was added to water and the insoluble material was filtered. The filtrate was slightly acidified with concentrated hydrochloric acid and extracted with methylene chloride. Then the solution was dried over anhydrous sodium sulfate, and the solvent was distilled off, yielding 0.26 g of the desired compound with a melting point of 152 to 155°C.

Examples of synthesis no. 2 to 13

The same procedure as in Synthesis Example no. 1, and the obtained results are presented in Table 2.

Table 2

[image] [image]

Note: The numbers of intermediates in the pyridine column and the numbers of compounds in the product column are given in relation to the same from Tables 1 and 3.

Example of synthesis no. 14

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

Method 1

A solution of 250 mg of 2-amino-4,6-dimethoxypyrimidine, 0.65 g of triethylamine, and 2.5 g of ethyl acetate was added dropwise to 6.9 g of an ethyl acetate solution containing 20% phosgene at 15°C. , and the mixture was maintained at 15°C for one hour. Then the mixture was heated to 90°C in an oil bath, and the excess of phosgene and ethyl acetate was distilled off. A solution of 300 mg of 2-aminosulfonyl-N,N-dimethylnicotinamide in 10 ml of acetonitrile was then prepared and added dropwise to the above mixture, and 0.2 g of triethylamine was then also added dropwise. The resulting mixture was reacted at room temperature for one hour.

After completion of the reaction, the product was added to water and acidified with hydrochloric acid, and the precipitated crystals were filtered. The crystals were washed with water and dried to give 0.46 g of the desired product.

Method 2

/I/ 2.12 g of 2-aminosulfonyl-N,N-dimethylnicotinamide was added to 5 ml of a dimethylformamide suspension containing 60% sodium hydride at -5°C, and the resulting mixture was reacted for about one hour. 10 ml of dimethylformamide solution and 2.14 g of diphenyl carbonate were added dropwise to the above solution at -5°C. The solution was warmed to room temperature for about 30 minutes to complete the reaction. The reaction solution was added to water and washed with methylene chloride. The aqueous layer was acidified with hydrochloric acid, and then extracted with methylene chloride. The methylene chloride layer was dried with anhydrous sodium sulfate, and the methylene chloride was distilled off under reduced pressure. The obtained crystals were recrystallized from ethyl acetate and hexane and 0.91 g of N,N-dimethyl-2-phenoxycarbonylaminosulfonylnicotinamide with a melting point of 189 to 194°C was obtained.

/II/ 0.28 g of N,N-dimethyl-2-phenoxycarbonyl-aminosulfonylnicotinamide prepared by procedure /I/ and 0.14 g of 2-amino-4-chloro-6-methoxypyrimidine were added to 8 ml of anhydrous dioxane, and the obtained mixture reacted under reflux conditions for about 40 minutes.

After completion of the reaction, the reaction mixture was added to 200 ml of water, and the resulting crystals were filtered to obtain 0.21 g of N-(4-chloro-6-methoxypyrimidin-2-yl)aminocarbonyl/-3-dimethylaminocarbonyl-2 -pyridinesulfonamide, which has a melting point of 157 to 158.5°C.

/III/ 18.3 mg of sodium metal was added to 7 ml of anhydrous methanol, and then 0.11 g of N-(4-chloro-6-methoxypyrimidin-2-yl)aminocarbonyl/-3-dimethylaminocarbonyl-2- of pyridinesulfonamide prepared in the above procedure /II/. The resulting mixture was heated and refluxed for 12 hours.

After completion of the reaction, the reaction mixture was added to water and acidified with hydrochloric acid, and the precipitated crystals were filtered, washed with water, and dried, so that 70 mg of the desired product was obtained.

Typical compounds represented by the general formula (I) and their salts according to the present invention will be shown in Table 3.

Table 3

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The compounds of this invention show herbicidal effects against various weeds: Cyperaceae weeds such as rice sedge (Cyperus iria), Japanese knotweed (Scirpus juncoides), and purple sedge (Cyperus rotudus); grasses (Gramineae) such as bearded millet (Echinochloa crus-galli), magpie (Digitaria adscendens), green fly (Setaria viridis), powdery mildew (Eleusine indica), wild oats (Avena fatua), corn (Sorghum halepense), and sedge (Agropyron repens); and broad-leaved weeds such as mallow (Abutilon theophrasti), garden sedge (Ipomoea purpurea), common loboda (Chenopodium album), (Sida spinosa), common defiance (Portulaca oleracea), sedge (Amaranthus viridis), sickle root (Cassia tora) , sedum (Solanum nigrum), water sedum (Polygonum longisetum), bramble (Stellaria media), thistle (Xanthium strumarium), and sedge (Cardamine flexuosa).

Therefore, the herbicides of the present invention will find application in farms and agricultural fields, for example, orchards and mulberry fields, and non-agricultural fields, for example, forests, alleys, playgrounds, hippodromes, parks. The herbicidal compositions of this invention can be applied by soil treatment or foliar treatment, if desired.

The compounds of the present invention can separately have herbicidal effects against harmful weeds in cereals and can be used effectively. The herbicidal compound of this invention is applied as granules, enema powder, emulsion concentrate or aqueous solutions prepared by mixing the compounds with a carrier as well as with additives such as diluent, solvent, emulsifier, dispersant or surfactant, as appropriate. A suitable mixing ratio of active substance to agricultural additives is between 1:99 and 90:10, and preferably between 5:95 and 60:40 by weight. The optimum amount of active ingredient to be used cannot be absolutely determined as it varies depending on various factors such as climatic conditions, soil conditions, the form of the chemical, the type of weed to be controlled, or the duration of application, but the amount of active ingredient is usually 0.1 up to 100 g per are, preferably from 0.2 to 50 g, and even better from 0.5 g to 10 g.

The herbicidal composition of this invention can be mixed or used together with other agricultural chemicals, fertilizers, soil or protective agents. Such applications provide approximately the same or better effects or actions. Examples of other herbicides that can be mixed with the herbicidal composition of this invention are listed below. In some cases, a synergistic effect can be achieved.

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)acetanilide

2-chloro-6'-ethyl-N-(2-methoxy-1-methylethyl)aceto-o-toluidide

2-chloro-N-isopropylacetanilide

2-chloro-N,N-di-2-propenylacetamide

S-ethyldipropylthiocarbamate

S-Ethyldiisobutylthiocarbamate

S-propyldipropylthiocarbamate

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

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-methylcarbamate

3,5-dibromo-4-hydroxybenzonitrile

2-chloro-4-trifluoromethylphenyl-3-ethoxy-4-nitrophenylether.

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 together with 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)acetanilide, 2-chloro-6'-ethyl- N-(2-methoxy-1-methylethyl)aceto-o-toluidide or N-(1-ethoxypropyl)-2,6-dinitro-3,4-xylide. The herbicide of this combination is not harmful to cereals and makes it possible to kill weeds almost completely.

Example of testing 1

Plots of 1/1,500 acre were stocked with topsoil and pre-determined amounts of seed of various test plants were planted. When the test plants reached a predetermined growth stage (ie 2.2- to 3.5-leaf stage for corn (Zea mays), 2.0- to 3.5-leaf stage for wheat (Triticum aestium), 2.0- to 3.5-leaf stage for Sida spinosa, 0.5- to 1.2-leaf stage for garden sedge, 0.5- to 1.2-leaf stage for watercress, 0.1- to 1.5-leaf stage for horsetail, and 2.0- to 2.5-leaf stage for whiskered millet), water was prepared dispersion by diluting a wetting powder containing a predetermined amount of each of the tested compounds with 5 L/acre of water, and 0.2% agricultural dispersant was added to the aqueous solution. The resulting solution was applied to the leaves of the plants with a small sprayer. Twenty-two or thirty-seven days after application, the degree of plant growth was visually observed. Weed control is expressed on a 10-point scale where 10 indicates that the plant was completely destroyed and 1 indicates that there was no effect, as shown below in Table 4.

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Example of testing 2

Particles of 1/10,000 are are adequately supplied with soil, and sown with magpie and helper. After that, when the test samples of sedge and helper reached the 2- and 0.5-leaf stage, the compound to be used was measured by determining the content of the active ingredient beforehand, and the compound was diluted in 5 L of water per acre. To this aqueous solution was added 0.2% agricultural spray agent, and the resulting solution was sprayed with a sprayer. The growth rate of magpie and helper was visually checked after 23 days, and weed control was expressed in the same manner as in Test Example 1. The results are shown in Table 5.

Table 5

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Example of testing 3

Two 15 cm long roots of corn plant were sown on a plot of 1/3000 are in the greenhouse. When the grass reached the 4- to 5-leaf stage, the compounds to be used were measured by taking a predetermined amount, and the compounds were diluted with 5 liters of water per acre. In addition, 0.2% agricultural spray agent was added to this aqueous solution, and the resulting solution was sprayed on the leaves and stems of the plants. Thirty-five days after application, visual control of this grass was carried out. Weed control was expressed in the same manner as in Test Example 1, and the results are shown below in Table 6.

Table 6

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Example of testing 4

Four sprouted purple nightshade roots were planted on a 1/10,000 acre plot in a greenhouse. When the nightshade reached the 3- to 4-leaf stage, the compounds to be used were measured by determining the active ingredient content beforehand, and the compounds were diluted with 5 liters of water per acre. In addition, 0.2% agricultural spray agent was added to this aqueous solution, and the resulting solution was sprayed on the leaves of the plants. Fifty-one days after application, weeds were visually controlled for purple nightshade. Weed control was expressed in the same manner as in Test Example 1, and the results are shown below in Table 7.

Table 7

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Examples of formulation of herbicidal compositions according to this invention will be described below.

Preparation example 1 parts by weight

(1) Kaolinite powder 97

(2) Polyoxyethylene octyphenyl ether 2

(3) Connection no. 15 1

The above ingredients are mixed and turned into a powder.

Example of preparation 2 parts by weight

(1) Water-soluble starch 55

(2) Sodium lignosulfate 5

(3) Connection no. 59 40

The above ingredients were mixed and turned into a powder from which an aqueous solution was made.

Example of preparation 3 parts by weight

(1) Kaolin 78

(2) Condensation product of sodium naphthalene sulfonate and formalin 2

(3) Polyoxyethylenealkylallylethanesulfonate 5

(4) Silica micropowder 15

Ingredients (1) to (4) were mixed with the compounds of the present invention at a mixing ratio of 9:1 to obtain a wetting powder.

Example of preparation 4 parts by weight

(1) Diatomaceous earth 63

(2) Polyoxyethylenealkylphenylethersulfate ammonium salt 5

(3) Dialkyl sulfosuccinate 2

(4) Connection no. 29 30

The above ingredients were mixed and a moisturizing powder was obtained.

Example of preparation 5 parts by weight

(1) Micropowder of milovka 33

(2) Dialkyl sulfosuccinate 3

(3) Polyoxyethylene alkyl sulfate 4

(4) Connection no. 34 60

The above ingredients are mixed to prepare a moisturizing powder.

Example of preparation 6 parts by weight

(1) Sodium phenylsulfonate 4

(2) Sodium polycarboxylate 3

(3) Sodium alkylarylsulfonate 1

(4) Kaolin 12

(5) Connection no. 25 80

The above ingredients were mixed with the addition of water, after drying they were crushed and a moisturizing powder was created.

Claims (20)

1. Substituted pyridinesulfonamide compound and its salt, characterized by the fact that it is represented by the following general formula: [image] group, each of R2 and R2 independently represents a halogen atom, an alkyl group, a haloalkyl group, an alkenyl group, an alkynyl group, an alkoxyl group, a haloalkoxyl group, an alkoxyalkyl group, a haloalkoxyalkyl group, a cycloalkyl group, a halocycloalkyl group, an alkoxycarbonyl group, a haloalkoxycarbonyl group, a phenyl group or a halophenyl group, with the proviso that when one of R1 and R2 represents a hydrogen atom, the other represents one of the groups other than a hydrogen atom; R1 and R2 together with the adjacent nitrogen atom can form a heterocyclic ring; Y represents a halogen atom, an alkyl group, a haloalkyl group, an alkyl group, a haloalkyl group, an alkylthio group, a haloalkylthio group, an alkoxyalkyl group, haloalkoxyalkyl group, or [image] group (wherein R 3 and R 4 each independently represent a hydrogen atom or an alkyl group); n is 0, or an integer of 1 or 2; and each of X1 and X2 independently represents a methyl group, a methoxyl group, or an ethoxyl group. 2. The compound according to claim 1, characterized in that the pyridinesulfonamide compound or its salt is a substituted pyridinesulfonamide and its salt represented by the following formula [image] wherein R1, R2, Y, n, X1 and X2 are the same as in claim 1. 3. A compound or its salt according to claim 2, characterized in that R1 is a hydrogen atom or an alkyl group, R2 is an alkyl group, Y is a halogen atom, an alkyl group, a haloalkyl group, an alkyl group, an alkoxyalkyl group, n is 0 or 1, and each of X1 and X2 are independently methoxyl groups. 4. A compound or its salt according to claim 2, characterized in that R1 is a hydrogen atom or a methyl group, R2 is a methyl group, Y is a chlorine atom, a bromine atom, a methyl group or a difluoromethyl group and Y is in position 6 of the pyridine ring, n is 0 or 1, and each of X1 and X2 are independently methoxy groups. 5. The compound according to claim 2, characterized in that the compound is 6-bromo-N-(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl/-3-dimethylaminocarbonyl-2-pyridinesulfonamide. 6. The compound according to claim 2, characterized in that the compound is 6-difluoromethyl-N-(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl/-3-dimethylaminocarbonyl-2-pyridinesulfonamide. 7. The compound according to claim 2, characterized in that the compound is N-(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl/-3-dimethylaminocarbonyl-2-pyridinesulfonamide. 8. The compound according to claim 2, characterized in that the compound is N-(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl/-3-dimethylaminocarbonyl-6-methyl-2-pyridinesulfonamide. 9. The compound according to claim 2, characterized in that the compound is 6-chloro-N-(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl/-3-dimethylaminocarbonyl-2-pyridinesulfonamide. 10. The compound according to claim 2, characterized in that the compound is N-(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl/-3-methylaminocarbonyl-2-pyridinesulfonamide. 11. The compound according to claim 2, characterized in that the compound is a salt, the sodium salt of N-(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl/-3-dimethylaminocarbonyl-2-pyridinesulfonamide. 12. Herbicidal composition, characterized in that it mainly consists of a herbicidally effective amount of the compound or its salt specified in claim 1, and an agriculturally acceptable additive. 13. The preparation according to claim 12, characterized in that the mixing ratio of the substituted pyridinesulfonamide compound and its salt according to the agriculturally acceptable additive is 1:99 to 90:10. 14. Method for destroying harmful weeds in cereal fields by application, characterized in that the preparation according to claim 12 is in the amount of 0.1 to 100 g/acre based on the active ingredient. 15. Process for the production of a substituted pyridinesulfonamide compound or its salt, characterized by the fact that it is represented by the following general formula: [image] group, where each of R1 and R2 independently represents a hydrogen atom, an alkyl group, a haloalkyl group, an alkenyl group, an alkynyl group, an alkoxyl group, a haloalkyl group, an alkoxyalkyl group, a haloalkoxy alkyl group, a cycloalkyl group, a halocycloalkyl group, an alkoxycarbonyl group, a haloalkoxycarbonyl group , a phenyl group or a halophenyl group, with the proviso that when one of R1 and R2 represents a hydrogen atom, the other represents one of the groups other than a hydrogen atom; R1 and R2 together with the adjacent nitrogen atom can form a heterocyclic ring; Y represents a halogen atom, an alkyl group, a haloalkyl group, an alkyl group, a haloalkyl group, an alkylthio group, a haloalkylthio group, an alkoxyalkyl group, haloalkoxyalkyl group, or [image] group (wherein R 3 and R 4 each independently represent a hydrogen atom or an alkyl group); n is 0, or an integer of 1 or 2; and each of X1 and X2 independently represents a methyl group, a methoxyl group, or an ethoxyl group, characterized in that it comprises the reaction of a pyridine compound represented by the following general formula: R - SO2Z1 in which R has the meanings given above, Z1 represents an NH2 group, -NCO group, -NHCOCI group or -NHCOOR5 (where R5 represents an alkyl group or an aryl group) with a pyrimidine compound represented by the following general formula: [image] wherein each of X3 and X4 independently represents a halogen atom, a methyl group, a methoxyl group, or an ethoxyl group, Z2 represents an NH2 group, -NCO group, -NHCOCI group, or -NHCOOR5 group (wherein R5 represents as defined above), with the proviso that when Z1 represents an NH2 group, Z2 represents an -NCO group, -NHCOCI group, or -NHCOOR5 group, and that when Z2 represents an NH2 group, Z1 represents an -NCO group, -NHCOCI group, or -NHCOOR5 group; then carrying out methoxylation or ethoxylation when X3 and/or X4 represents a halogen atom; and if desired, treatment for the formation of salt. 16. The method according to claim 15, characterized in that Z1 represents -NH2 group, and Z2 represents -NCO group, -NHCOCI group, or -NHCOOR5 group. 17. The method according to claim 15, characterized in that Z1 represents -NCO group, -NHCOCI group, -NHCOOR5 group, and Z2 represents NH2 group. 18. The method according to claim 15, characterized in that the reaction temperature in the condensation reaction is -20 to +100°C. 19. A pyridine compound as an intermediate product, characterized by the fact that it is represented by the following general formula: RSO2Z1 in which R represents [image] group or [image] group, where each of R1 and R2 independently represents a hydrogen atom, an alkyl group, a haloalkyl group, an alkenyl group, an alkynyl group, an alkoxyl group, a haloalkyl group, an alkoxyalkyl group, a haloalkoxyalkyl group, a cycloalkyl group, a halocycloalkyl group, an alkyloxycarbonyl group, a haloalkoxycarbonyl group, a phenyl group or a halophenyl group, with the proviso that when one of R1 and R2 represents a hydrogen atom, the other represents one of the groups other than a hydrogen atom; R1 and R2 together with the adjacent nitrogen atom can form a heterocyclic ring; Y represents a halogen atom, an alkyl group, a haloalkyl group, an alkyl group, a haloalkyl group, an alkylthio group, a haloalkylthio group, an alkoxyalkyl group, haloalkoxyalkyl group, or [image] group (wherein R 3 and R 4 each independently represent a hydrogen atom or an alkyl group); and n is 0, or an integer of 1 or 2; and Z 1 is an NH 2 group or a -NCO group, a -NHCOCl group, or -NHCOOR 5 (wherein R 5 is an alkyl group or an aryl group). 20. Compound according to claim 19, characterized in that R [image] 20. group, (in which R1, R2, Y and n have the same meanings as in claim 19).