Ethanol → Ethyl 3-oxo-3,4-dihydro-2H-1,4-benzoxazine-6-carboxylate

3-oxo-3,4-dihydro-2H-1,4-benzoxazine-6-carboxylic acid, (1.63 g, 8.4 mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (1.49 g, 7.8 mmol), 1-hydroxybenzotriazole hydrate (1.05 g, 7.8 mmol), and 4-dimethylaminopyridine (0.43 g, 3.5 mmol), were dissolved in 40 mL of anhydrous dichloromethane under argon. Triethylamine (4.0 mL, 29 mmol) was added to the room temperature mixture via syringe. Absolute ethanol (0.83 mL, 14.2 mmol) was then delivered to the solution, which was maintained at room temperature for 18 hours. HPLC (Eclipse XDB-C18, 4.6×250 mm, 5 micron, 1-99% CH3CN/H2O with 0.1% trifluoroacetic acid) chromatogram indicated that all of the starting material (Rt=3.7 min) was gone and that a single new product had formed (Rt=5.5 min). The solvent was removed by rotary evaporation and the residue was dissolved in 200 mL of ethyl acetate. The organic layer was washed with water (3×50 mL), 10% hydrochloric acid solution (3×50 mL), and 50% sodium bicarbonate solution (3×50 mL). The organic phase was dried over Na2SO4, filtered and concentrated to give ethyl 3-oxo-3,4-dihydro-2H-1,4-benzoxazine-6-carboxylate (1.6 g, 7.2 mmol, 86%) as a yellow solid. MS (ES) m/e 221 [M+H]+.

1. customhad formed (Rt=5.5 min)
2. customThe solvent was removed by rotary evaporation
3. dissolutionthe residue was dissolved in 200 mL of ethyl acetate
4. washThe organic layer was washed with water (3×50 mL), 10% hydrochloric acid solution (3×50 mL), and 50% sodium bicarbonate solution (3×50 mL)
5. dry with materialThe organic phase was dried over Na2SO4
6. filtrationfiltered
7. concentrationconcentrated

ORDレコード

ord-0adef128679942e6ac60b5fabe3bfaba

出典データセット

uspto-grants-2010_07

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US07749998B2