N,N,N',N'-Tetramethylethylenediamine → 1,2,3,3a,8,8a-Hexahydro-alpha-oxo-1,3a,8-trimethyl-5-pyrrolo[2,3-b]indole acetic acid, diethyl amide

HRID 258151

反応式

HRID 258151 の反応式
C([Li])(CC)C.CN(CCN(C)C)C.Br[C:15]1[CH:16]=[C:17]2[C:21](=[CH:22][CH:23]=1)[N:20]([CH3:24])[CH:19]1[N:25]([CH3:28])[CH2:26][CH2:27][C:18]21[CH3:29].[CH2:30]([N:32]([C:35](=[O:41])[C:36](OCC)=[O:37])[CH2:33][CH3:34])[CH3:31]>CCOCC>[CH2:30]([N:32]([CH2:33][CH3:34])[C:35](=[O:41])[C:36](=[O:37])[C:15]1[CH:16]=[C:17]2[C:21](=[CH:22][CH:23]=1)[N:20]([CH3:24])[CH:19]1[N:25]([CH3:28])[CH2:26][CH2:27][C:18]21[CH3:29])[CH3:31]

参加物

6

反応物 4

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 138489Ethyl N,N-diethyloxamateHCID 197825615-Bromo-1,2,3,3a,8,8a-hexahydro-1,3a,8-trimethylpyrrolo[2,3-b]indoleHCID 178418400CID 53628100

生成物 1

HCID 867464261,2,3,3a,8,8a-Hexahydro-alpha-oxo-1,3a,8-trimethyl-5-pyrrolo[2,3-b]indole acetic acid, diethyl amide

試薬・触媒・溶媒 1

HCID 3283Diethyl Ether溶媒3 回

反応条件

温度
-78 °C

実験手順

To a stirred (-78° C.) solution of sec-butyllithium (1.3M in cyclohexane; 6.6 ml) and TMEDA (1.3 ml) in anhydrous ether (4.0 ml) was added via canula under a N2 atmosphere a solution of 5-bromo-1,2,3,3a,8,8a-hexahydro-1,3a,8-trimethylpyrrolo[2,3-b]indole (1.69 g), in anhydrous ether (4.0 ml). The solution was stirred at -78° C. for 2.5 hours and then added via canula, under N2, to a stirred (-78° C.) solution of N,N-diethylamino-oxo-acetic acid, ethyl ester (3.6 g) in diethyl ether (8.0 ml). The solution was stirred at -78° C. for 3 hours and gradually allowed to warm to room temperature over 2 hours. The mixture was quenched by the addition of an aqueous solution of saturated NH4Cl. The organic phase was separated and washed with two 50 ml portions of an aqueous solution of saturated NaHCO3, with brine, and dried (Na2SO 4). The crude residue was purified using preparative HPLC (silica gel, loading and eluting with 3% methanol in dichloromethane). The appropriate fractions were combined and concentrated to a foam which solidified upon trituration with hexane, to afford 1,2,3,3a,8,8a-hexahydro-α-oxo-1,3a,8-trimethyl-5-pyrrolo[2,3-b]indole acetic acid, diethyl amide.

後処理

  1. additionadded via canula, under N2
  2. stirringThe solution was stirred at -78° C. for 3 hours
  3. temperatureto warm to room temperature over 2 hours
  4. customThe mixture was quenched by the addition of an aqueous solution of saturated NH4Cl
  5. customThe organic phase was separated
  6. washwashed with two 50 ml portions of an aqueous solution of saturated NaHCO3, with brine
  7. dry with materialdried (Na2SO 4)
  8. customThe crude residue was purified
  9. washHPLC (silica gel, loading and eluting with 3% methanol in dichloromethane)
  10. concentrationconcentrated to a foam which

出典と根拠

ORDレコード
ord-394388e3bd33474681e284d8bbae3804
出典データセット
uspto-grants-1993_11
特許番号
US05264587

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