1,4-Dioxane → 1,1-dimethylethyl 7-(4-amino-3-nitrophenyl)-2,3-dihydro-1,4-benzoxazepine-4(5H)-carboxylate

温度

95 °C

(4-{[(1,1-dimethylethyl)oxycarbonyl}-2,3,4,5-tetrahydro-1,4-benzoxazepin-7-yl)boronic acid (example 1, step 2) (2.22 g, 7.57 mmol) and 4-bromo-2-nitroaniline (1.56 g, 7.20 mmol) were taken into dioxane (20 mL), water (4 mL) and DIPEA (5.4 mL, 31 mmol) followed by addition of dichloro[1,1-bis(diphenylphosphino]ferrocenepalladium (II) dichloromethane adduct (322 mg, 0.39 mmol) and the mixture was heated to 95° C. for 2 h. The mixture was cooled to room temperature and partitioned with ethyl acetate and 10% aqueous citric acid. The biphasic mixture was filtered through a celite pad and the organic filtrate was washed once with 0.5M aqueous hydrochloric acid, brine then dried over anhydrous magnesium sulfate, filtered and concentrated. The residue was purified by silica gel chromatography to give 1,1-dimethylethyl 7-(4-amino-3-nitrophenyl)-2,3-dihydro-1,4-benzoxazepine-4(5H)-carboxylate (2.01 g, 69% yield) as a yellow crystalline solid.

1. temperatureThe mixture was cooled to room temperature
2. custompartitioned with ethyl acetate and 10% aqueous citric acid
3. filtrationThe biphasic mixture was filtered through a celite pad
4. washthe organic filtrate was washed once with 0.5M aqueous hydrochloric acid, brine
5. dry with materialthen dried over anhydrous magnesium sulfate
6. filtrationfiltered
7. concentrationconcentrated
8. customThe residue was purified by silica gel chromatography

ORDレコード

ord-b6f0056e96de490e9cea155ea9f9a963

出典データセット

uspto-grants-2014_01

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US08637499B2