反応 #502109

反応方程式

sodium bicarbonate

2-((2-hydroxyethyl)sulfinyl)ethyl(2S)-2-(6-methoxy(2-naphthyl))propanoate

acetic anhydride

nitric acid

→

ethyl(2S)-2-(6-methoxy(2-naphthyl))propanoate

収率 22.0%

溶媒

ethyl acetate

ethyl acetate

反応条件

後処理

1. 1
   workup.ADDITIONAfter addition
2. 2
   workup.STIRRINGthe mixture was stirred at 0° C. for 5 minutes
3. 3
   workup.STIRRINGThe reaction mixture was stirred at 0° C. for 10 minutes
4. 4
   workup.ADDITIONpoured into
5. 5
   温度a pre-cooled
6. 6
   workup.STIRRINGThe mixture was stirred cold for 20 minutes
7. 7
   その他The reaction mixture was partitioned between ethyl acetate and water
8. 8
   洗浄washed with sodium bicarbonate, water, and brine
9. 9
   乾燥dried over sodium sulfate
10. 10
    その他The solvent was evaporated
11. 11
    その他the residue was purified by column chromatography on silica
12. 12
    洗浄eluting with methanol/ethyl acetate (gradient, 0% to 20%)

実験手順

To acetic anhydride (9.1 mL, 98.1 mmol) at 0° C. was added fuming nitric acid (90%, 2.86 mL, 61.3 mmol) with stirring. After addition was complete, the mixture was stirred at 0° C. for 5 minutes, then added drop-wise to a solution of the product of Example 1a (4.10 g, 12.3 mmol) in ethyl acetate (20 mL) at 0° C. The reaction mixture was stirred at 0° C. for 10 minutes, then poured into a pre-cooled (0° C.) mixture of 25 mL of ethyl acetate and 50 mL of sodium bicarbonate. The mixture was stirred cold for 20 minutes, and then warmed to room temperature for 1 hour. The reaction mixture was partitioned between ethyl acetate and water, washed with sodium bicarbonate, water, and brine, and dried over sodium sulfate. The solvent was evaporated and the residue was purified by column chromatography on silica, eluting with methanol/ethyl acetate (gradient, 0% to 20%), gave 2-((2-nitrooxy)ethyl)sulfinyl)ethyl(2S)-2-(6-methoxy(2-naphthyl))propanoate as a pale yellow solid (1.07 g, 22% yield) and 2-((2-hydroxyethyl)sulfinyl)ethyl(2S)-2-(6-methoxy(2-naphthyl))propanoate as a white solid. 2-((2-hydroxyethyl)sulfinyl)ethyl(2S)-2-(6-methoxy(2-naphthyl))propanoate (1.87 g, 44% yield). Mp 74-86° C. 1H NMR (300 MHz, CDCl3) δ 7.70 (d, J=8.6 Hz, 2H), 7.65 (d, J=1.0 Hz, 1H), 7.37 (dt, J=1.9, 8.5 Hz, 1H), 7.15 (dd, J=2.5, 8.8 Hz, 1H), 7.11 (d, J=2.3 Hz, 1H), 4.52 (m, 2H), 3.91 (s, 3H), 3.87 (q, J=7.2 Hz, 1H), 2.97 (m, 2H), 2.84 (br.s, 1H), 2.62 (m, 2H), 1.59 (d, J=7.2 Hz, 3H) Mass spectrum (API-TIS) m/z 351 (MH+).

出典