Sodium hydride → Ethyl 1-amino-4-bromo-5-cyano-1H-pyrrole-2-carboxylate

HRID 1972809

반응식

HRID 1972809 반응식
[Br:1][C:2]1[CH:3]=[C:4]([C:9]([O:11][CH2:12][CH3:13])=[O:10])[NH:5][C:6]=1[C:7]#[N:8].[H-].[Na+].[NH2:16]OP(=O)(C1C=CC=CC=1)C1C=CC=CC=1.C([O-])(O)=O.[Na+]>CN(C=O)C>[NH2:16][N:5]1[C:6]([C:7]#[N:8])=[C:2]([Br:1])[CH:3]=[C:4]1[C:9]([O:11][CH2:12][CH3:13])=[O:10]

참가 물질

6

반응물 4

HCID 24758Sodium hydrideHCID 516892Sodium BicarbonateHCID 10955453O-(Diphenylphosphinyl)hydroxylamineHCID 58529640ethyl 4-bromo-5-cyano-1H-pyrrole-2-carboxylate

생성물 1

HCID 58529285Ethyl 1-amino-4-bromo-5-cyano-1H-pyrrole-2-carboxylate수율 100%

시약·촉매·용매 1

HCID 6228Dimethylformamide용매2회

실험 절차

To a solution of ethyl 4-bromo-5-cyano-1H-pyrrole-2-carboxylate (2.70 g, 11.1 mmol) in DMF (75 mL) was added 95% sodium hydride powder (323 mg, 12.8 mmol). The mixture was stirred (rt) for 20 min, then (aminooxy)(diphenyl)phosphine oxide (3.89 g, 16.7 mmol) was added in one portion. After 15 min, the reaction mixture became thick and additional DMF (25 mL) was added. The reaction was heated (50° C.) for 3 h and was allowed to cool to rt and stir for 17 h. The reaction was poured into saturated aqueous NaHCO3 solution (200 mL) and was extracted with ethyl acetate (3×100 mL). The combined organics were washed with water (2×100 mL), dried (Na2SO4) and were concentrated to dryness to afford 2.8 g (100%) of the desired product, which contained minor impurities. 1H NMR (300 MHz, DMSO-d6) δ 6.95 (s, 1 H), 6.57 (s, 2 H), 4.28 (q, 2 H), 1.29 (t, 3 H).

후처리

  1. waitAfter 15 min
  2. temperatureThe reaction was heated (50° C.) for 3 h
  3. temperatureto cool to rt
  4. stirringstir for 17 h
  5. extractionwas extracted with ethyl acetate (3×100 mL)
  6. washThe combined organics were washed with water (2×100 mL)
  7. dry with materialdried (Na2SO4)
  8. concentrationwere concentrated to dryness

출처 및 근거

ORD 기록
ord-328b3215d9bb43a1965be4ca42c50a7c
출처 데이터셋
uspto-grants-2013_04
특허 번호
US08431695B2

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