1-methoxy-N,N,N',N'-tetramethylmethanediamine

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:85.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 4-acetylpyridine (25 ml, 226.0 mmol) and bis(dimethylamino)methoxymethane (44 ml, 293.8 mmol) was heated at 85° C. for 30 min followed by evaporation to dryness to recover a solid of 3-(dimethylamino)-1-(4-pyridyl)-3-propen-1-one. Its ethanolic solution (200 ml) was transferred into ethanolic 1.13 N sodium ethoxide (200 ml) containing urea (16.3 g, 271 mmol). The mixture was heated to reflux overnight, then cooled down to ice-bath temperature. The precipitate was filtered, dissolved in a minimal amount of water and the aqueous solution was washed with dichloromethane. The title compound was precipitated from the aqueous solution by neutralization with 6N hydrochloric acid and filtered. More material was obtained from the original reaction filtrate which was concentrated, diluted with a minimal amount of water and washed with dichloromethane. The aqueous solution was neutralized with 6N hydrochloric acid and the precipitate filtered. MS (m/z): 174.1 (M+H)+; C9H7N3O requir. 173.2. followed by evaporation to dryness to recover a solid of 3-(dimethylamino)-1-(4-pyridyl)-3-propen-1-one The mixture was heated to reflux overnight cooled down to ice-bath temperature The precipitate was filtered dissolved in a minimal amount of water the aqueous solution was washed with dichloromethane The title compound was precipitated from the aqueous solution by neutralization with 6N hydrochloric acid filtered More material was obtained from the original reaction filtrate which was concentrated diluted with a minimal amount of water washed with dichloromethane the precipitate filtered

反応条件: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: According to a modified literature procedure (Wasserman, H. H.; Ives, J. L. J. Org. Chem. 1985, 50, 3573-3580) a solution of 1.0 g (3.9 mmol) of (4-benzyloxy-phenyl)-acetic acid methyl ester in 4 mL of toluene was flushed with argon. To this solution was added 0.842 mL g (5.5 mmol) of methoxy bis(dimethylamino)methane, and the resulting mixture was stirred at 65° C. under argon overnight. The reaction mixture was concentrated to give 1.21 g of desired 2-(4-benzyloxy-phenyl)-3-dimethylamino-acrylic acid methyl ester as indicated by 1H NMR (containing traces of starting material). The product was used without any further purification in the next step. was flushed with argon To this solution was added 0.842 mL The reaction mixture was concentrated

反応条件: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: According to a modified literature procedure (Wasserman, H. H.; Ives, J. L. J. Org. Chem. 1985, 50, 3573-3580) a solution of 1.0 g (3.9 mmol) of (4-benzyloxy-phenyl)-acetic acid methyl ester in 4 mL of toluene was flushed with argon. To this solution was added 0.842 mL g (5.5 mmol) of methoxy bis(dimethylamino)methane, and the resulting mixture was stirred at 65° C. under argon overnight. The reaction mixture was concentrated to give 1.21 g of desired 2-(4-benzyloxy-phenyl)-3-dimethylamino-acrylic acid methyl ester as indicated by 1H NMR (containing traces of starting material). The product was used without any further purification in the next step. was flushed with argon To this solution was added 0.842 mL The reaction mixture was concentrated

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

実験手順: 1-Triphenylmethyl-4-piperidone (0.239 g, 0.70 mmol) was added to methoxybis(dimethylamino)methane (1.75 ml) and the reaction mixture was stirred at 50° for sixteen hours. Volatiles were then removed in vacuo to provide a yellow solid, which was triturated with ether, and air dried to give the title product as a light yellow solid (0.179 g, 0.45 mmol, 64% yield). Volatiles were then removed in vacuo to provide a yellow solid, which was triturated with ether, and air dried

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

実験手順: 1-Triphenylmethyl-4-piperidone (0.239 g, 0.70 mmol) was added to methoxybis(dimethylamino)methane (1.75 ml) and the reaction mixture was stirred at 50° for sixteen hours. Volatiles were then removed in vacuo to provide a yellow solid, which was triturated with ether, and air dried to give the title product as a light yellow solid (0.179 g, 0.45 mmol, 64% yield). Volatiles were then removed in vacuo to provide a yellow solid, which was triturated with ether, and air dried

反応条件: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: According to a modified literature procedure (Wasserman, H. H.; Ives, J. L. J. Org. Chem. 1985, 50, 3573–3580) a solution of 1.0 g (3.9 mmol) of (4-benzyloxy-phenyl)-acetic acid methyl ester in 4 mL of toluene was flushed with argon. To this solution was added 0.842 mL g (5.5 mmol) of methoxy bis(dimethylamino)methane, and the resulting mixture was stirred at 65° C. under argon overnight. The reaction mixture was concentrated to give 1.21 g of desired 2-(4-benzyloxy-phenyl)-3-dimethylamino-acrylic acid methyl ester as indicated by 1H NMR (containing traces of starting material). The product was used without any further purification in the next step. was flushed with argon To this solution was added 0.842 mL The reaction mixture was concentrated

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

実験手順: To 4 parts of 2-(2H-1,4-benzothiazin-3(4H)-ylidene)-2-(4-fluorophenyl)acetamide in 80 parts of DMF is added 6 parts dimethylformamide diethyl acetal and the reaction mixture was stirred at room temperature for 2 to 6 hours then heated at 80°-140° C. for 1 to 6 hours. After cooling 6 parts of methoxy-bis-(dimethylamino)methane is added and the reaction mixture then heated at 50° to 80° C. for 2 to 24 hrs. The cooled reaction mixture is then diluted with 40 parts of water and refluxed for 2 to 18 hr. Upon cooling the precipitate present was collected and recrystallized from aqueous DMF to give 4-(4-fluorophenyl)-5H-pyrido[3,4-b][1,4]benzothiazin-3(2H)-one which melts above 300°. then heated at 80°-140° C. for 1 to 6 hours is added the reaction mixture then heated at 50° to 80° C. for 2 to 24 hrs The cooled reaction mixture refluxed for 2 to 18 hr Upon cooling the precipitate present was collected recrystallized from aqueous DMF

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

実験手順: To 4 parts of 2-(2H-1,4-benzothiazin-3(4H)-ylidene)-2-(4-fluorophenyl)acetamide in 80 parts of DMF is added 6 parts dimethylformamide diethyl acetal and the reaction mixture was stirred at room temperature for 2 to 6 hours then heated at 80°-140° C. for 1 to 6 hours. After cooling 6 parts of methoxy-bis-(dimethylamino)methane is added and the reaction mixture then heated at 50° to 80° C. for 2 to 24 hrs. The cooled reaction mixture is then diluted with 40 parts of water and refluxed for 2 to 18 hr. Upon cooling the precipitate present was collected and recrystallized from aqueous DMF to give 4-(4-fluorophenyl)-5H-pyrido[3,4-b][1,4]benzothiazin-3(2H)-one which melts above 300°. then heated at 80°-140° C. for 1 to 6 hours is added the reaction mixture then heated at 50° to 80° C. for 2 to 24 hrs The cooled reaction mixture refluxed for 2 to 18 hr Upon cooling the precipitate present was collected recrystallized from aqueous DMF

反応条件: temp:85.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 4-acetylpyridine (25 ml, 226.0 mmol) and bis(dimethylamino)methoxymethane (44 ml, 293.8 mmol) was heated at 85° C. for 30 min followed by evaporation to dryness to recover a solid of 3-(dimethylamino)-1-(4-pyridyl)-3-propen-1-one. Its ethanolic solution (200 ml) was transferred into ethanolic 1.13 N sodium ethoxide (200 ml) containing urea (16.3 g, 271 mmol). The mixture was heated to reflux overnight, then cooled down to ice-bath temperature. The precipitate was filtered, dissolved in a minimal amount of water and the aqueous solution was washed with dichloromethane. The title compound was precipitated from the aqueous solution by neutralization with 6N hydrochloric acid and filtered. More material was obtained from the original reaction filtrate which was concentrated, diluted with a minimal amount of water and washed with dichloromethane. The aqueous solution was neutralized with 6N hydrochloric acid and the precipitate filtered. MS (m/z): 174.1 (M+H)+; C9H7N3O requir. 173.2. followed by evaporation to dryness to recover a solid of 3-(dimethylamino)-1-(4-pyridyl)-3-propen-1-one The mixture was heated to reflux overnight cooled down to ice-bath temperature The precipitate was filtered dissolved in a minimal amount of water the aqueous solution was washed with dichloromethane The title compound was precipitated from the aqueous solution by neutralization with 6N hydrochloric acid filtered More material was obtained from the original reaction filtrate which was concentrated diluted with a minimal amount of water washed with dichloromethane the precipitate filtered

反応条件: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: According to a modified literature procedure (Wasserman, H. H.; Ives, J. L. J. Org. Chem. 1985, 50, 3573-3580) a solution of 1.0 g (3.9 mmol) of (4-benzyloxy-phenyl)-acetic acid methyl ester in 4 mL of toluene was flushed with argon. To this solution was added 0.842 mL g (5.5 mmol) of methoxy bis(dimethylamino)methane, and the resulting mixture was stirred at 65° C. under argon overnight. The reaction mixture was concentrated to give 1.21 g of desired 2-(4-benzyloxy-phenyl)-3-dimethylamino-acrylic acid methyl ester as indicated by 1H NMR (containing traces of starting material). The product was used without any further purification in the next step. was flushed with argon To this solution was added 0.842 mL The reaction mixture was concentrated

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

実験手順: 1-Triphenylmethyl-4-piperidone (0.239 g, 0.70 mmol) was added to methoxybis(dimethylamino)methane (1.75 ml) and the reaction mixture was stirred at 50° for sixteen hours. Volatiles were then removed in vacuo to provide a yellow solid, which was triturated with ether, and air dried to give the title product as a light yellow solid (0.179 g, 0.45 mmol, 64% yield). Volatiles were then removed in vacuo to provide a yellow solid, which was triturated with ether, and air dried