Diethyl chlorophosphate → Ethyl 4,5-Dihydro-4,4-dimethylimidazo[1,5-a]quinoxaline-3-carboxylate

HRID 1378755노트

반응식

HRID 1378755 반응식
[CH3:1][C:2]([CH3:5])([O-])[CH3:3].[K+].C([N:15]1[C:24]2[C:19](=[CH:20][CH:21]=[CH:22][CH:23]=2)[NH:18][C:17](=O)C1)(=O)C1C=CC=CC=1.P(Cl)(OCC)(OCC)=O.[N+:35]([CH2:37][C:38]([O:40][CH2:41][CH3:42])=[O:39])#[C-]>C1COCC1>[CH3:1][C:2]1([CH3:5])[NH:15][C:24]2[C:19](=[CH:20][CH:21]=[CH:22][CH:23]=2)[N:18]2[CH:17]=[N:35][C:37]([C:38]([O:40][CH2:41][CH3:42])=[O:39])=[C:3]12

참가 물질

6

반응물 4

HCID 13139Diethyl chlorophosphateHCID 533707Ethyl isocyanoacetateHCID 7343784-Benzoyl-1,2,3,4-tetrahydroquinoxalin-2-oneHCID 23665647Potassium tert-butoxide2회

생성물 1

HCID 54175730Ethyl 4,5-Dihydro-4,4-dimethylimidazo[1,5-a]quinoxaline-3-carboxylate

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

실험 절차

Potassium tert-butoxide (1M, 4.54 ml) is added to 1,2,3,4-tetrahydro-3,3-dimethylquinoxalin-2-one (IV, EXAMPLE 2, 0.762 g) in THF (4 ml) at ice/saline temperature. The reaction is stirred for 40 min, at which time diethyl chlorophosphate (0.656 ml) is added. After stirring at ice-saline temperature for 2 hr, ethyl isocyanoacetate (0.562 g) is added, followed by potassium t-butoxide (1M, 4.97 ml). The reaction is stirred for 3.5 hr, allowing it to slowly warm to 20°-25°. The reaction is then quenched with several drops of acetic acid and then partitioned between ethyl acetate, aqueous sodium bicarbonate and saline. The phases are separated and the organic phase is dried over magnesium sulfate, concentrated, and the resulting crude product chromatographed on silica gel (200 ml) eluting with methanol/dichloromethane (2/98). The appropriate fractions are pooled and concentrated to give the title compound, mp 145°-149°; NMR (CDCl3) 1.44, 1.74, 3.79, 4.40, 6.77, 6.82, 7.10, and 7.39 δ.

후처리

  1. additionis added
  2. stirringThe reaction is stirred for 3.5 hr
  3. temperatureto slowly warm to 20°-25°
  4. customThe reaction is then quenched with several drops of acetic acid
  5. custompartitioned between ethyl acetate, aqueous sodium bicarbonate and saline
  6. customThe phases are separated
  7. dry with materialthe organic phase is dried over magnesium sulfate
  8. concentrationconcentrated
  9. customthe resulting crude product chromatographed on silica gel (200 ml)
  10. washeluting with methanol/dichloromethane (2/98)
  11. concentrationconcentrated

출처 및 근거

ORD 기록
ord-823c0ef6cb274995bb33229b78aa3f63
출처 데이터셋
uspto-grants-1997_09
특허 번호
US05668282

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