반응 #1054104

반응 방정식

H2O

3,4-Methylenedioxynitrobenzene

sodium cyanide

NaOH

sodium cyanide

→

compound 477A

수율 64.0%

2-Cyano-5-nitrophenol

수율 64.0%

용매

HMPA

반응 조건

후처리

1. 1
   온도The reaction was maintained at 150° C. for 45 min
2. 2
   온도cooled
3. 3
   추출The aqueous layer was extracted with ether (2×25 mL)
4. 4
   workup.ADDITIONThe basic aqueous layer was carefully acidified to pH 4 by addition of 10% HCl
5. 5
   추출extracted with ether (3×25 mL)
6. 6
   세척The combined organic layers were washed with brine (25 mL)
7. 7
   건조dried over sodium sulfate
8. 8
   농축concentrated in vacuo
9. 9
   기타Purification by flash chromatography on silica gel eluting with 5% MeOH/CH2Cl2

실험 절차

3,4-Methylenedioxynitrobenzene (1.67 g, 10.0 mmol) was dissolved in 20 mL of HMPA and sodium cyanide (0.49 g, 10.0 mmol) was added. The reaction was heated to 150° C. under nitrogen and three portions of sodium cyanide (0.245 g, 5.00 mmol, total) were added over 15 min. The reaction was maintained at 150° C. for 45 min, cooled, and poured into 50 mL of H2O followed by the addition of 50 mL of 5% NaOH. The aqueous layer was extracted with ether (2×25 mL) and the organic layer was discarded. The basic aqueous layer was carefully acidified to pH 4 by addition of 10% HCl and extracted with ether (3×25 mL). The combined organic layers were washed with brine (25 mL), dried over sodium sulfate and concentrated in vacuo. Purification by flash chromatography on silica gel eluting with 5% MeOH/CH2Cl2 gave 1.05 g (64%) of compound 477A as a yellow-brown solid. HPLC: 91.6% at 1.03 min (retention time) (Phenomenex column, 30×4.6 mm, 10-90% aqueous methanol over 2 min containing 0.1% TFA, 5 mL/min, monitoring at 220 nm. MS (ES): m/z 165.23 [M+H]+.

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