반응 #502109

반응 방정식

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

수율 22.0%

용매

ethyl acetate

ethyl acetate

반응 조건

후처리

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
   온도a pre-cooled
6. 6
   workup.STIRRINGThe mixture was stirred cold for 20 minutes
7. 7
   기타The reaction mixture was partitioned between ethyl acetate and water
8. 8
   세척washed with sodium bicarbonate, water, and brine
9. 9
   건조dried over sodium sulfate
10. 10
    기타The solvent was evaporated
11. 11
    기타the residue was purified by column chromatography on silica
12. 12
    세척eluting with methanol/ethyl acetate (gradient, 0% to 20%)

실험 절차

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+).

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