Method for producing fused heterocyclic compound

Abstract

A compound represented by formula (4) is produced by a step A of reacting a compound represented by formula (2): ##STR00001##
wherein R.sup.1 represents an ethyl group or the like, R represents a halogen atom or the like, n represents 0, 1, 2, or 3, and M represents potassium or the like, with thionyl chloride to obtain a compound represented by formula (1): ##STR00002##
a step B of reacting the compound represented by formula (1) with a compound represented by formula (5): ##STR00003##
wherein A.sup.1 represents a nitrogen atom or CH, R.sup.5 represents a trifluoromethyl group or the like, and m represents 1 or 2, to produce a compound represented by formula (3): ##STR00004##
or an acid salt thereof; and a step C of reacting the compound represented by formula (3) or an acid salt thereof in the presence of acid at 100 C. to 180 C. to obtain the compound represented by formula (4): ##STR00005##

Claims

1. A method for producing a compound represented by formula (4), which comprises a step A of reacting a compound represented by formula (2): ##STR00036## wherein R.sup.1 represents a chain hydrocarbon group having 1 to 6 carbon atoms which is optionally halogenated, or an alicyclic hydrocarbon group having 3 to 6 carbon atoms which is optionally halogenated, each R independently represents a chain hydrocarbon group having 1 to 6 carbon atoms which is optionally halogenated, or a halogen atom, n represents 0, 1, 2, or 3, and M represents sodium, potassium, or lithium, with thionyl chloride to obtain a compound represented by formula (1): ##STR00037## wherein R.sup.1, R, and n have the same meanings as defined above; a step B of reacting the compound represented by formula (1) with a compound represented by formula (5): ##STR00038## wherein A.sup.1 represents a nitrogen atom or CH, R.sup.5 represents a chain hydrocarbon group having 1 to 6 carbon atoms which is optionally halogenated, or an alicyclic hydrocarbon group having 3 to 6 carbon atoms which is optionally halogenated, and m represents 1 or 2, to produce a compound represented by formula (3): ##STR00039## wherein R.sup.1, R, R.sup.5, A.sup.1, m, and n have the same meanings as defined above; and a step C of reacting the compound represented by formula (3) or an acid salt thereof in the presence of an acid at 100 C. to 180 C. to obtain the compound represented by formula (4): ##STR00040## wherein R.sup.1, R, R.sup.5, A.sup.1, m, and n have the same meanings as defined above.

2. The method according to claim 1, wherein the acid in the step C is a sulfonic acid compound.

3. The method according to claim 1, wherein the acid in the step C is p-toluenesulfonic acid.

4. The method according to claim 1, wherein the acid in the step C is methanesulfonic acid.

5. A method for producing a compound represented by formula (3) or an acid salt thereof, which comprises a step A of reacting a compound represented by formula (2): ##STR00041## wherein R.sup.1 represents a chain hydrocarbon group having 1 to 6 carbon atoms which is optionally halogenated, or an alicyclic hydrocarbon group having 3 to 6 carbon atoms which is optionally halogenated, each R independently represents a chain hydrocarbon group having 1 to 6 carbon atoms which is optionally halogenated, or a halogen atom, n represents 0, 1, 2, or 3, and M represents sodium, potassium, or lithium, with thionyl chloride to obtain a compound represented by formula (1): ##STR00042## wherein R.sup.1, R, and n have the same meanings as defined above; and a step B of reacting the compound represented by formula (1) with a compound represented by formula (5): ##STR00043## wherein A.sup.1 represents a nitrogen atom or CH, R.sup.5 represents a chain hydrocarbon group having 1 to 6 carbon atoms which is optionally halogenated, or an alicyclic hydrocarbon group having 3 to 6 carbon atoms which is optionally halogenated, and m represents 1 or 2, to produce the compound represented by formula (3): ##STR00044## wherein R.sup.1, R, R.sup.5, A.sup.1, m, and n have the same meanings as defined above.

6. The method according to claim 1, wherein the solvent used in the step B contains comprises an ether solvent.

7. A method for producing a compound represented by formula (1), which comprises a step A of reacting a compound represented by formula (2): ##STR00045## wherein R.sup.1 represents a chain hydrocarbon group having 1 to 6 carbon atoms which is optionally halogenated, or an alicyclic hydrocarbon group having 3 to 6 carbon atoms which is optionally halogenated, each R independently represents a chain hydrocarbon group having 1 to 6 carbon atoms which is optionally halogenated, or a halogen atom, n represents 0, 1, 2, or 3, and M represents sodium, potassium, or lithium, with thionyl chloride to obtain the compound represented by formula (1): ##STR00046## wherein R.sup.1, R, and n have the same meanings as defined above.

Description

EXAMPLES

(1) The present invention will be further described by way of Examples, but the present invention is not limited to these Examples.

Example 1

(2) ##STR00019##

(3) Under a nitrogen atmosphere, 0.50 g of potassium (3-ethylsulfonyl)-2-pyridinecarboxylate, 2.50 g of xylene, and 0.01 g of N,N-dimethylformamide were mixed and heated to 60 C., and then 0.35 g of thionyl chloride was added dropwise over 5 hours, followed by stirring at 60 C. for 4 hours. To the reaction solution, isobutylamine was added and quantitative determination was carried out by an internal reference method (internal reference substance; biphenyl) using high-performance liquid chromatography to obtain (3-ethylsulfonyl)-2-pyridinecarboxylic chloride at a yield of 95.1%.

Example 2

(4) ##STR00020##

(5) Under a nitrogen atmosphere, 25.00 g of xylene, 0.07 g of N,N-dimethylformamide, and 4.80 g of thionyl chloride were mixed and heated to 60 C., and then 5.00 g of potassium (3-ethylsulfonyl)-2-pyridinecarboxylate was added over 5 hours, followed by stirring at 60 C. for 4 hours. To the reaction solution, isobutylamine was added and quantitative determination was carried out by an internal reference method (internal reference substance; biphenyl) using high-performance liquid chromatography to obtain (3-ethylsulfonyl)-2-pyridinecarboxylic chloride at a yield of 96.9%.

Example 3

(6) ##STR00021##

(7) 2-Amino-4-(trifluoromethylsulfinyl)phenol was prepared by the following method.

(8) A mixture of 5.0 g of 2-nitro-4-(trifluoromethylsulfinyl) phenol, 0.50 g of palladium-carbon (Pd 5%), and 65 ml of ethanol was stirred under a hydrogen atmosphere at 35 C. for 6 hours. The reaction mixture allowed to cool down to room temperature was filtered through Celite (registered trademark) and water was added, followed by extraction with ethyl acetate. The organic layer was washed with water, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The resulting solid was washed with chloroform to obtain 3.87 g of 2-amino-4-(trifuloromethylsulfinyl)phenol.

(9) Under a nitrogen atmosphere, 1.80 g of 2-amino-4-(trifluoromethylsulfinyl)phenol and 9.00 g of tetrahydrofuran were mixed and cooled to 0 C., and then a mixture of 1.95 g of (3-ethylsulfonyl)-2-pyridinecarboxylic chloride and 3.90 g of xylene was added dropwise over one hour, followed by stirring at 0 C. for 4 hours. To the reaction mixture, an aqueous saturated sodium hydrogen carbonate solution was added and the mixture was extracted with ethyl acetate, and then the organic layer was concentrated under reduced pressure to obtain 3-ethylsulfonyl-N-[2-hydroxy-5-(trifluoromethylsulfinyl)phenyl]picolinamide at a yield of 95.6%. .sup.1H-NMR (DMSO-d.sub.6) : 11.47 (1H, brs), 10.42 (1H, s), 8.97 (1H, dd), 8.74 (1H, s), 8.43 (1H, d), 7.88 (1H, dd), 7.58 (1H, dd), 7.25 (1H, d), 3.68 (2H, q), 1.18 (3H, t).

Example 4

(10) ##STR00022##

(11) Under a nitrogen atmosphere, a mixture of 1.00 g of 3-ethylsulfonyl-N-[2-hydroxy-5-(trifluoromethylsulfinyl)phenyl]picolinamide, 0.66 g of p-toluenesulfonic acid monohydrate, and 5.00 g of xylene was dehydrated under reflux at 155 C. for 20 hours. The reaction mixture allowed to cool down to room temperature was added to an aqueous saturated sodium hydrogen carbonate solution. After separation, 5.00 g of heptane was added to the organic layer and cooling crystallization was carried out to obtain 2-(3-ethylsulfonyl pyridin-2-yl)-5-(trifluoromethylsulfinyl)benzoxazole at a yield of 88.2%.

(12) .sup.1H-NMR (CDCl.sub.3) : 9.04 (1H, dd), 8.61 (1H, dd), 8.35 (1H, d), 7.96-7.86 (2H, m), 7.77 (1H, dd), 4.01 (2H, q), 1.44 (3H, t).

Example 5

(13) ##STR00023##

(14) Under a nitrogen atmosphere, a mixture of 0.30 g of 3-ethylsulfonyl-N-[2-hydroxy-5-(trifluoromethylsulfinyl)phenyl]picolinamide, 0.20 g of p-toluenesulfonic acid monohydrate, and 1.50 g of mesitylene was dehydrated under reflux at 180 C. for 7 hours. The reaction mixture allowed to cool down to room temperature was added to an aqueous saturated sodium hydrogen carbonate solution. After separation, the resulting organic layer was analyzed by internal reference method (internal reference substance; biphenyl) using high-performance liquid chromatography to obtain 2-(3-ethylsulfonyl pyridin-2-yl)-5-(trifluoromethylsulfinyl)benzoxazole at a yield of 81.8%.

Example 6

(15) ##STR00024##

(16) Under a nitrogen atmosphere, 1.80 g of 2-amino-4-(trifluoromethylsulfonyl)phenol and 9.00 g of tetrahydrofuran were mixed. After cooling to 0 C., a mixture of 1.91 g of (3-ethylsulfonyl)-2-pyridinecarboxylic chloride and 3.82 g of xylene was added dropwise over one hour, followed by stirring at 0 C. for 4 hours. To the reaction mixture, an aqueous saturated sodium hydrogen carbonate solution was added and the mixture was extracted with ethyl acetate, and then the organic layer was concentrated under reduced pressure to obtain 3-ethylsulfonyl-N-[2-hydroxy-5-(trifluoromethylsulfonyl)phenyl]picolinamide at a yield of 96.7%. .sup.1H-NMR (DMSO-d.sub.6) : 12.66 (1H, brs), 10.42 (1H, s), 8.97 (1H, dd), 8.85 (1H, d), 8.43 (1H, dd), 7.88 (1H, dd), 7.82 (1H, dd), 7.32 (1H, d), 3.68 (2H, q), 1.19 (3H, t).

Example 7

(17) ##STR00025##

(18) Under a nitrogen atmosphere, 10.00 g of 2-amino-4-(trifluoromethylsulfonyl)phenol and 50.00 g of tetrahydrofuran were mixed and cooled to 0 C., and then a mixture of 12.35 g of (3-ethylsulfonyl)-2-pyridinecarboxylic chloride and 27.00 g of tetrahydrofuran was added dropwise over one hour, followed by stirring at 0 C. for 4 hours. To the reaction mixture, an aqueous saturated sodium hydrogen carbonate solution was added, and then the mixture was concentrated under reduced pressure. The residue was extracted with ethyl acetate and the organic layer was concentrated under reduced pressure to obtain 3-ethylsulfonyl-N-[2-hydroxy-5-(trifluoromethylsulfonyl)phenyl]picolinamide at a yield of 93.4%.

Example 8

(19) ##STR00026##

(20) Under a nitrogen atmosphere, a mixture of 1.00 g of 3-ethylsulfonyl-N-[2-hydroxy-5-(trifluoromethylsulfonyl)phenyl]picolinamide, 0.62 g of p-toluenesulfonic acid monohydrate, and 5.00 g of xylene was dehydrated under reflux at 155 C. for 15 hours. The reaction mixture allowed to cool down to room temperature was added to an aqueous saturated sodium hydrogen carbonate solution. After separation, 5.00 g of heptane was added to the organic layer and cooling crystallization was carried out to obtain 2-(3-ethylsulfonylpyridin-2-yl)-5-(trifluoromethylsulfonyl) benzoxazole at a yield of 86.5%.

(21) .sup.1H-NMR (CDCl.sub.3) : 9.05 (1H, dd), 8.61 (1H, dd), 8.59 (1H, d), 8.17 (1H, dd), 7.96 (1H, d), 7.80 (1H, dd), 3.98 (2H, q), 1.45 (3H, t).

Example 9

(22) ##STR00027##

(23) Under a nitrogen atmosphere, 2.70 g of 2-amino-4-(trifluoromethylsulfinyl)phenol and 8.10 g of tetrahydrofuran were mixed and cooled to 0 C., and then a mixture of 3.64 g of (3-ethylsulfonyl)-2-pyridinecarboxylic chloride and 3.64 g of tetrahydrofuran was added dropwise over 4 hours, followed by stirring at 0 C. for 12 hours. The reaction mixture was concentrated under reduced pressure to obtain 6.21 g of 3-ethylsulfonyl-N-[2-hydroxy-5-(trifluoromethylsulfinyl)phenyl]picolinamide hydrochloride at a yield of 96.7%.

(24) ##STR00028##

(25) .sup.1H-NMR (DMSO-d.sub.6) : 12.56 (1H, brs), 10.40 (1H, s), 8.97 (1H, dd), 8.86 (1H, d), 8.44 (1H, dd), 7.88 (1H, dd), 7.81 (1H, dd), 7.42 (1H, d), 3.68 (2H, q), 1.20 (3H, t).

Example 10

(26) ##STR00029##

(27) Under a nitrogen atmosphere, a mixture of 3.00 g of 3-ethylsulfonyl-N-[2-hydroxy-5-(trifluoromethylsulfinyl)phenyl]picolinamide hydrochloride, 1.24 g of p-toluenesulfonic acid monohydrate, and 15.00 g of xylene was dehydrated under reflux at 155 C. for 20 hours. The reaction mixture allowed to cool down to room temperature was added to an aqueous saturated sodium hydrogen carbonate solution. After separation, quantitative determination of the resulting organic layer was carried out by internal reference method (internal reference substance; biphenyl) using high-performance liquid chromatography to obtain 2-(3-ethylsulfonyl pyridin-2-yl)-5-(trifluoromethylsulfinyl)benzoxazole at a yield of 85.0%.

Example 11

(28) ##STR00030##

(29) Under a nitrogen atmosphere, 3.00 g of 2-amino-4-(trifluoromethylsulfinyl)phenol and 12.00 g of tetrahydrofuran were mixed and cooled to 0 C., and then a mixture of 4.11 g of (3-ethylsulfonyl)-2-pyridinecarboxylic chloride and 7.00 g of xylene was added dropwise over 4 hours, followed by stirring at 0 C. for 12 hours. The reaction mixture was concentrated under reduced pressure and a mixture of 5.06 g of p-toluenesulfonic acid monohydrate and xylene 16.90 g of xylene was added to the resulting the residue, followed by dehydration under reflux at 155 C. for 24 hours. The reaction mixture allowed to cool down to room temperature was added to an aqueous saturated sodium hydrogen carbonate solution. After separation, quantitative determination of the resulting organic layer was carried out by internal reference method (internal reference substance; biphenyl) using high-performance liquid chromatography to obtain 2-(3-ethylsulfonylpyridin-2-yl)-5-(trifluoromethylsulfinyl)benzoxazole at a yield of 79.4%.

Example 12

(30) ##STR00031##

(31) Under a nitrogen atmosphere, 4.33 g of 2-amino-4-(trifluoromethylsulfinyl)phenol and 34.72 g of tetrahydrofuran were mixed and cooled to 0 C., and then a mixture of 5.30 g of (3-ethylsulfonyl)-6-chloro-2-pyridinecarboxylic chloride and 10.60 g of tetrahydrofuran was added dropwise over one hour, followed by stirring at 0 C. for 4 hours. To the reaction mixture, an aqueous saturated sodium hydrogen carbonate solution was added and the mixture was extracted with ethyl acetate, and then the organic layer was concentrated under reduced pressure to obtain 3-ethylsulfonyl-N-[2-hydroxy-5-(trifluoromethylsulfinyl)phenyl]picolinamide at a yield of 99.2%.

(32) .sup.1H-NMR (DMSO-d.sub.6) : 11.55 (1H, brs), 10.45 (1H, s), 8.65 (1H, s), 8.38 (1H, d), 7.96 (1H, d), 7.57 (1H, d), 7.26 (1H, d), 3.84 (2H, q), 1.32 (3H, t).

Example 13

(33) ##STR00032##

(34) Under a nitrogen atmosphere, a mixture of 1.00 g of 3-ethylsulfonyl-6-chloro-N-[2-hydroxy-5-(trifluoromethylsulfinyl) phenyl]picolinamide, 0.74 g of p-toluenesulfonic acid monohydrate, and 5.21 g of chlorobenzene was dehydrated under reflux at 140 C. for 8 hours. The reaction mixture allowed to cool down to room temperature was added to an aqueous saturated sodium hydrogen carbonate solution. After separation, the organic layer was concentrated to obtain 0.95 g of 2-(6-chloro-3-ethylsulfonylpyridine-2-yl)-5-(trifluoromethylsulfinyl) benzoxazole.

(35) .sup.1H-NMR (CDCl.sub.3) : 8.53 (1H, d), 8.36 (1H, d), 7.94 (1H, dd), 7.89 (1H, dd), 7.76 (1H, d), 4.01 (2H, q), 1.44 (3H, t).

Example 14

(36) ##STR00033##

(37) Under a nitrogen atmosphere, 4.58 g of 2-amino-4-(trifluoromethylsulfonyl)phenol and 36.82 g of tetrahydrofuran were mixed and cooled to 0 C., and then a mixture of 5.30 g of (3-ethylsulfonyl)-6-chloro-2-pyridinecarboxylic chloride and 10.60 g of tetrahydrofuran was added dropwise over one hour, followed by stirring at 0 C. for 4 hours. To the reaction mixture, an aqueous saturated sodium hydrogen carbonate solution was added and the mixture was extracted with ethyl acetate, and then the organic layer was concentrated under reduced pressure to obtain 3-ethylsulfonyl-6-chloro-N-[2-hydroxy-5-(trifluoromethylsulfonyl)phenyl]picolinamide at a yield of 98.4%.

(38) .sup.1H-NMR (DMSO-d.sub.6) : 10.77 (1H, brs), 9.97 (1H, s), 9.09 (1H, s), 8.49 (1H, d), 7.85 (1H, d), 7.77 (1H, d), 7.18 (1H, d), 3.80 (2H, q), 1.22 (3H, t).

Example 15

(39) ##STR00034##

(40) Under a nitrogen atmosphere, a mixture of 1.01 g of 3-ethylsufonyl-6-chloro-N-[2-hydroxy-5-(trifluoromethylsulfonyl) phenyl]picolinamide, 0.72 g of p-toluenesulfonic acid monohydrate, and 5.32 g of chlorobenzene was dehydrated under reflux at 140 C. for 8 hours. The reaction mixture allowed to cool down to room temperature was added to an aqueous saturated sodium hydrogen carbonate solution. After separation, the organic layer was concentrated to obtain 0.95 g of 2-(6-chloro-3-ethylsulfonylpyridine-2-yl)-5-(trifluoromethylsulfonyl) benzoxazole.

(41) .sup.1H-NMR (CDCl.sub.3) : 8.59 (1H, d), 8.54 (1H, d), 8.18 (1H, dd), 7.98 (1H, d), 7.79 (1H, d), 3.98 (2H, q), 1.45 (3H, t).

Comparative Example 1

(42) ##STR00035##

(43) Under a nitrogen atmosphere, 3.00 g of (3-ethylsulfonyl)-2-pyridinecarboxylic acid, 9.00 g of toluene, and 0.11 g of N,N-dimethylformamide were mixed and heated to 60 C., and then 2.03 g of thionyl chloride was added dropwise over 5 hours, followed by stirring at 60 C. for 4 hours. To the reaction solution, n-butanol was added and analysis was carried out using high-performance liquid chromatography to obtain (3-ethylsulfonyl)-2-pyridinecarboxylic chloride at a yield of 65.3%.

INDUSTRIAL APPLICABILITY

(44) The present invention provides a method for producing a compound represented by formula (4) which has an excellent control efficacy against pests.