2,2-dimethylchromen-6-amine

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

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

実験手順: A solution of 6-nitro-2,2-dimethyl-2H-benzopyran (prepared as described in Evans et al., J. Med. Chem.) (4.65 g, 22.66 mmoles) and SnCl2. 2H2O (25.57 g, 0.11 mole) in ethanol (46.5 ml) was heated at reflux for 45 minutes. The reaction mixture was poured onto ice/H2O (180 g), made basic (pH 10-11) with 50% sodium hydroxide solution, and extracted with ethyl acetate. The organic phase was washed with saturated sodium chloride solution, dried over sodium sulfate, and evaporated in vacuo to obtain 3.88 g of the title A compound as a brown oil. at reflux for 45 minutes The reaction mixture was poured onto ice/H2O (180 g) extracted with ethyl acetate The organic phase was washed with saturated sodium chloride solution dried over sodium sulfate evaporated in vacuo

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

実験手順: A solution of 6-nitro-2,2-dimethyl-2H-benzopyran (prepared as described in Evans et al., J. Med. Chem.) (4.65 g, 22.66 mmoles) and SnCl2. 2H2O (25.57 g, 0.11 mole) in ethanol (46.5 ml) was heated at reflux for 45 minutes. The reaction mixture was poured onto ice/H2O (180 g), made basic (pH 10-11) with 50% sodium hydroxide solution, and extracted with ethyl acetate. The organic phase was washed with saturated sodium chloride solution, dried over sodium sulfate, and evaporated in vacuo to obtain 3.88 g of the title A compound as a brown oil. at reflux for 45 minutes The reaction mixture was poured onto ice/H2O (180 g) extracted with ethyl acetate The organic phase was washed with saturated sodium chloride solution dried over sodium sulfate evaporated in vacuo

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

実験手順: A solution of 6-nitro-2,2-dimethyl-2H-benzopyran (prepared as described in Evans et al., J. Med. Chem.) (4.65 g, 22.66 mmoles) and SnCl2. 2H2O (25.57 g, 0.11 mole) in ethanol (46.5 ml) was heated at reflux for 45 minutes. The reaction mixture was poured onto ice/H2O (180 g), made basic (pH 10-11) with 50% sodium hydroxide solution, and extracted with ethyl acetate. The organic phase was washed with saturated sodium chloride solution, dried over sodium sulfate, and evaporated in vacuo to obtain 3.88 g of the title A compound as a brown oil. at reflux for 45 minutes The reaction mixture was poured onto ice/H2O (180 g) extracted with ethyl acetate The organic phase was washed with saturated sodium chloride solution dried over sodium sulfate evaporated in vacuo

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

実験手順: To a stirred solution of 20 g (0.11 mol) of 6-amino-2,2-dimethylbenzopyran and 70 g (0.91 mol) of ammonium acetate in 190 mL of acetic acid and 770 mL of MeOH at 65° C. is added dropwise over 0.5 h, a mixture of 11.1 g (0.14 mol) of formaldehyde and 20g (0.14 mol) of glyoxal. The mixture is stirred for 1 hour at 65° C., then poured onto 800 g of ice. The pH of the solution is adjusted to 10 by the addition of concentrated ammonium hydroxide. The mixture is extracted with dichloromethane (3×200 mL) and the combined organic extracts are dried with sodium sulfate, filtered and evaporated under reduced pressure. The resulting oil is subjected to chromatography on silica gel utilizing 3% methanol in dichloromethane as eluent. The eluates are analyzed utilizing thin layer chromatography and appropriate fractions are combined and evaporated to produce the title compound. The mixture is extracted with dichloromethane (3×200 mL) the combined organic extracts are dried with sodium sulfate filtered evaporated under reduced pressure evaporated

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

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

実験手順: To a stirred solution of 20 g (0.11 mol) of 6-amino-2,2-dimethylbenzopyran and 70 g (0.91 mol) of ammonium acetate in 190 mL of acetic acid and 770 mL of MeOH at 65° C. is added dropwise over 0.5 h, a mixture of 11.1 g (0.14 mol) of formaldehyde and 20g (0.14 mol) of glyoxal. The mixture is stirred for 1 hour at 65° C., then poured onto 800 g of ice. The pH of the solution is adjusted to 10 by the addition of concentrated ammonium hydroxide. The mixture is extracted with dichloromethane (3×200 mL) and the combined organic extracts are dried with sodium sulfate, filtered and evaporated under reduced pressure. The resulting oil is subjected to chromatography on silica gel utilizing 3% methanol in dichloromethane as eluent. The eluates are analyzed utilizing thin layer chromatography and appropriate fractions are combined and evaporated to produce the title compound. The mixture is extracted with dichloromethane (3×200 mL) the combined organic extracts are dried with sodium sulfate filtered evaporated under reduced pressure evaporated

反応条件: temp:180.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Under nitrogen atmosphere, to a solution of 6-amino-2,2-dimethylchromene (3.88 g, 22.1 mmol) and ruthenium trichloride (55.0 mg, 0.265 mmol) in dimethylene glycol dimethyl ether (8 mL), 1,3-propanediol (0.639 mL, 8.84 mmol) and tri-n-butyl phosphine (0.132 mL, 0.530 mmol) were added at room temperature, and the resulting mixture was stirred at 180° C. for 5 hours. Upon the completion of the reaction, ruthenium complex was removed by florisil column, and solvent was distilled off. The residue was purified by medium pressure column chromatography (hexane/ethyl acetate=5/1) and the aimed product was obtained (yield: 59%). Upon the completion of the reaction, ruthenium complex was removed by florisil column, and solvent was distilled off The residue was purified by medium pressure column chromatography (hexane/ethyl acetate=5/1)

反応条件: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To 6-amino-2,2-dimethylchromene (1.00 g, 5.71 mmol), 35% hydrochloric acid (1.43 mL, 17.1 mmol), p-chloranil (1.40 g, 5.71 mmol) and n-butanol (1.3 mL) were added at room temperature and the temperature was increased to 120° C. A solution of crotyl aldehyde (0.567 mL, 6.84 mmol) in n-butanol (0.52 mL) was added and the resulting mixture was stirred at 120° C. for 20 minutes. A solution of zinc chloride (0.777 g, 5.71 mmol) in tetrahydrofuran (10 mL) was added, and the resulting mixture was stirred at 120° C. for 20 minutes. Upon the completion of the reaction, sodium hydrogencarbonate aqueous solution was added, and the resulting solution was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. After distilling off the solvent, the residue was purified by column chromatography (hexane/ethyl acetate=2/1), and recrystallized with ethyl acetate to obtain the aimed product (yield: 22%). the resulting mixture was stirred at 120° C. for 20 minutes was added the resulting solution was extracted with ethyl acetate dried over anhydrous magnesium sulfate After distilling off the solvent the residue was purified by column chromatography (hexane/ethyl acetate=2/1) recrystallized with ethyl acetate

反応条件: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To 6-amino-2,2-dimethylchromene (1.00 g, 5.71 mmol), 35% hydrochloric acid (1.43 mL, 17.1 mmol), p-chloranil (1.40 g, 5.71 mmol) and n-butanol (1.3 mL) were added at room temperature and the temperature was increased to 120° C. A solution of crotyl aldehyde (0.567 mL, 6.84 mmol) in n-butanol (0.52 mL) was added and the resulting mixture was stirred at 120° C. for 20 minutes. A solution of zinc chloride (0.777 g, 5.71 mmol) in tetrahydrofuran (10 mL) was added, and the resulting mixture was stirred at 120° C. for 20 minutes. Upon the completion of the reaction, sodium hydrogencarbonate aqueous solution was added, and the resulting solution was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. After distilling off the solvent, the residue was purified by column chromatography (hexane/ethyl acetate=2/1), and recrystallized with ethyl acetate to obtain the aimed product (yield: 22%). the resulting mixture was stirred at 120° C. for 20 minutes was added the resulting solution was extracted with ethyl acetate dried over anhydrous magnesium sulfate After distilling off the solvent the residue was purified by column chromatography (hexane/ethyl acetate=2/1) recrystallized with ethyl acetate