(sulfinylamino)benzene

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 20 g (0.113 mole) of 3-trifluoromethyl-phenylhydrazine were dissolved in 50 ml of methanol with addition of 5 ml of acetic acid; 16 g (0.115 mole) of sulfinylaniline were added dropwise at a temperature of 22°C. The product crystallized out while the temperature rose to about 30°C. After filtration and drying, 16 g of N-sulfinyl-N-' -(3-trifluoromethylphenyl)-hydrazine of melting point 100°C were obtained. The yield was 64% of theory. The product crystallized out while the temperature rose to about 30°C After filtration drying

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 20 g (0.113 mole) of 3-trifluoromethyl-phenylhydrazine were dissolved in 50 ml of methanol with addition of 5 ml of acetic acid; 16 g (0.115 mole) of sulfinylaniline were added dropwise at a temperature of 22°C. The product crystallized out while the temperature rose to about 30°C. After filtration and drying, 16 g of N-sulfinyl-N-' -(3-trifluoromethylphenyl)-hydrazine of melting point 100°C were obtained. The yield was 64% of theory. The product crystallized out while the temperature rose to about 30°C After filtration drying

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 0.38 g of benzaldehyde and 120 g of ethyl 2-(2,1,3-benzothiadiazol-5-yl)-4-(4-methoxyphenyl)-4-oxo-butanoate ("A"), m.p. 89°, (obtainable by reaction of 5.5 g of ethyl 2-(2,1,3-benzothiadiazol-5-yl) acetate with 5.5 g of 2'-bromo-4-methoxyacetophenone and 4 g of potassium carbonate in 200 ml of acetone, 18 hours under reflux; ethyl 2-(2,1,3-benzothiadiazol-5-yl) acetate, m.p. 40-41°, is obtained by reaction of 24.3 g of ethyl 3,4-diaminophenyl acetate and 26.9 ml of thionylaniline in 80 ml of toluene, 4 hours under reflux) are added to a solution of 80 mg of sodium in 5 ml of methanol and the mixture is heated under reflux for one hour. After addition of 5 ml of acetic acid, it is heated for a further 16 hours. The solvent is removed and the residue is worked up in the customary manner. 3-(2,1,3-Benzothiadiazol-5-yl)-4-benzyl-5-hydroxy-5-(4-methoxy-phenyl)-5H-furan-2-one, FAB 431, is obtained. the mixture is heated under reflux for one hour is heated for a further 16 hours The solvent is removed

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A dinitrobenzene (I) is reacted with, for example, ammonium chloride and iron or with hydrogen gas and palladium on activated carbon in a solvent such as ethanol or toluene and at elevated temperature to give the corresponding aminoaniline (VII). The aminoaniline (VII) is reacted with, for example, thionyl chloride, N-thionyl aniline or sulfur dichloride in a solvent such as toluene or ethanol and at elevated temperature to yield a benzothiadiazole of formula (A'").

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 20 g (0.113 mole) of 3-trifluoromethyl-phenylhydrazine were dissolved in 50 ml of methanol with addition of 5 ml of acetic acid; 16 g (0.115 mole) of sulfinylaniline were added dropwise at a temperature of 22°C. The product crystallized out while the temperature rose to about 30°C. After filtration and drying, 16 g of N-sulfinyl-N-' -(3-trifluoromethylphenyl)-hydrazine of melting point 100°C were obtained. The yield was 64% of theory. The product crystallized out while the temperature rose to about 30°C After filtration drying

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 20 g (0.113 mole) of 3-trifluoromethyl-phenylhydrazine were dissolved in 50 ml of methanol with addition of 5 ml of acetic acid; 16 g (0.115 mole) of sulfinylaniline were added dropwise at a temperature of 22°C. The product crystallized out while the temperature rose to about 30°C. After filtration and drying, 16 g of N-sulfinyl-N-' -(3-trifluoromethylphenyl)-hydrazine of melting point 100°C were obtained. The yield was 64% of theory. The product crystallized out while the temperature rose to about 30°C After filtration drying

反応条件: temp:110.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 4-Fluoro-2,1,3-benzothiadiazole was synthesized according to the method in which N-thionylaniline (0.49 g, 3.5 mmol) was added to a solution of the 3-fluoro-O-phenylene diamine (200 mg, 1.6 mmol) in foluen (2 ml) The reaction mixture was heated at 100-120° C. for 4 hr. After the solvent was filtered off, the residue was dissolved in dichloromethane and the solution was washed with 10% HCl solution and water, successively. The organic layer was dried and evaporated to dryness. Purification by chromatography on a silica gel column with chloroform as an eluent gave 4-fluoro-2,1,3-benzothiadiazole as pal yellow oil. Confirmed data of the obtained chemical compound is shown as follows. 4-Fluoro-2,1,3-benzothiadiazole was synthesized After the solvent was filtered off the residue was dissolved in dichloromethane the solution was washed with 10% HCl solution and water The organic layer was dried evaporated to dryness Purification by chromatography on a silica gel column with chloroform as an eluent

反応条件: temp:110.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 4-Fluoro-2,1,3-benzothiadiazole was synthesized according to the method in which N-thionylaniline (0.49 g, 3.5 mmol) was added to a solution of the 3-fluoro-O-phenylene diamine (200 mg, 1.6 mmol) in foluen (2 ml) The reaction mixture was heated at 100-120° C. for 4 hr. After the solvent was filtered off, the residue was dissolved in dichloromethane and the solution was washed with 10% HCl solution and water, successively. The organic layer was dried and evaporated to dryness. Purification by chromatography on a silica gel column with chloroform as an eluent gave 4-fluoro-2,1,3-benzothiadiazole as pal yellow oil. Confirmed data of the obtained chemical compound is shown as follows. 4-Fluoro-2,1,3-benzothiadiazole was synthesized After the solvent was filtered off the residue was dissolved in dichloromethane the solution was washed with 10% HCl solution and water The organic layer was dried evaporated to dryness Purification by chromatography on a silica gel column with chloroform as an eluent

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: N-Thionylaniline (2.6 mL, 23.2 mmol) is added to amino(1-triphenylmethyl-1,4,5,6-tetrahydropyrimidin-5-yl)acetamide (1.64 g, 4.1 mmol) suspended in pyridine (25 ml). After heating at 90° C. for 48 hours the pyridine is evaporated, and the black residue partitioned between chloroform and water. The aqueous layer is lowered to pH 5 (HCl) and chromatographed (Dowex-50 W, 0.5 N ammonium hydroxide) to yield the product as a brown solid 1.05 g (61%) that can be further purified by chromatography (silica, methanol) and converted to a white crystalline hydrochloride salt, ms m/z=426. is evaporated the black residue partitioned between chloroform and water chromatographed (Dowex-50 W, 0.5 N ammonium hydroxide)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: N-Thionylaniline (2.6 mL, 23.2 mmol) is added to amino(1-triphenylmethyl-1,4,5,6-tetrahydropyrimidin-5-yl)acetamide (1.64 g, 4.1 mmol) suspended in pyridine (25 ml). After heating at 90° C. for 48 hours the pyridine is evaporated, and the black residue partitioned between chloroform and water. The aqueous layer is lowered to pH 5 (HCl) and chromatographed (Dowex-50W, 0.5N ammonium hydroxide) to yield the product as a brown solid 1.05 g (61%) that can be further purified by chromatography (silica, methanol) and converted to a white crystalline hydrochloride salt, ms m/z=426. is evaporated the black residue partitioned between chloroform and water chromatographed (Dowex-50W, 0.5N ammonium hydroxide)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 0.368 g of 4-cyclopentyloxy-3,5-dimethoxybenzaldehyde (“A”) and 0.52 g of ethyl 2-(2,1,3-benzothiadiazol-5-yl)-4-(4-methoxyphenyl)-4-oxobutanoate, m.p. 89° (obtainable by reaction of 5.5 g of ethyl 2-(2,1,3-benzothiadiazol-5-yl)acetate with 5.5 g of 2′-bromo-4-methoxyacetophenone and 4 g of potassium carbonate in 200 ml of acetone, 18 hours under reflux; ethyl 2-(2,1,3-benzothiadiazol-5-yl)acetate, m.p. 40-41° is obtained by reaction of 24.3 g of ethyl 3,4-diaminophenylacetate and 26.9 ml of thionylaniline in 80 ml of toluene, 4 hours under reflux) are added to a solution of 34 mg of sodium in 10 ml of ethanol and the mixture is heated under reflux for one hour. After addition of 1.4 ml of acetic acid, it is heated for a further 16 hours. The solvent is removed and the residue is worked up in the customary manner. 3-(2,1,3-Benzothiadiazol-5-yl)-4-(4-cyclopentyloxy-3,5-dimethoxy-benzyl)-5-hydroxy-5-(4-methoxyphenyl)-5H-furan-2-one is obtained, FAB 575. the mixture is heated under reflux for one hour is heated for a further 16 hours The solvent is removed

反応条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2,3-difluoro-1,4-di(2-thienyl)-5,6-diamino-benzene (1.2 g, 3.9 mmol) was added into a small flask and purged with Ar three times. Then, dry pyridine (24 ml), N-thionylaniline (1.08 g, 7.8 mmol) and chlorotrimethylsilane (0.76 g, 7.0 mmol) were added. The mixture was stirred at 80° C. for 16 h before poured into ice water. The yellow precipitate was then filtered and washed with a mixture of ethanol and water (1:1 v/v) to afford 5,6-difluoro-4,7-di(2-thienyl)-2,1,3-benzothiadiazole as a yellow solid (1.3 g, 98%). 1H and 19F NMR spectra were as expected. purged with Ar three times The yellow precipitate was then filtered washed with a mixture of ethanol and water (1:1 v/v)