Diisopropylamine → HCID 70071026、化合物

HRID 982030ノート

反応式

HRID 982030 の反応式
C(N[CH:5]([CH3:7])[CH3:6])(C)C.C([Li])CCC.[C:13]1(=[O:26])[C:18]2[NH:19][C:20]3[C:25]([C:17]=2[CH2:16][CH2:15][NH:14]1)=[CH:24][CH:23]=[CH:22][CH:21]=3.Br[CH:28]([CH2:34]CCC)[C:29]([O:31][CH2:32][CH3:33])=[O:30]>O1CCCC1>[CH2:32]([O:31][C:29]([CH:28]([CH2:7][CH2:5][CH3:6])[CH2:34][N:14]1[CH2:15][CH2:16][C:17]2[C:25]3[C:20](=[CH:21][CH:22]=[CH:23][CH:24]=3)[NH:19][C:18]=2[C:13]1=[O:26])=[O:30])[CH3:33]

参加物

6

反応物 4

HCID 7912DiisopropylamineHCID 79072Ethyl 2-bromohexanoateHCID 873712,3,4,9-Tetrahydro-1H-pyrido(3,4-b)indol-1-oneHCID 178418339Butyllithium

生成物 1

HCID 70071026HCID 70071026、化合物収率 39.1%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
0 °C

実験手順

A solution of 0.38 ml (2.8 mmol) of diisopropylamine in 25 ml of dry tetrahydrofuran was cooled under N2 atmosphere to -78° C. and treated with 1.1 ml (2.8 mmol) of n-butyllithium. The resulting solution was warmed to 0° C. for 5 min, recooled to -78° C. and treated with a solution of 250 mg (1.34 mmol) of 1,2,3,4-tetrahydro-9H-pyrido[3,4-b]indol-1-one (J. Chem. Soc. 1960, 4699) in 5 ml of tetrahydrofuran. The solution was allowed to warm to 0° C. followed by treatment with 0.25 ml (1.4 mmol) of ethyl 2-bromohexanoate. The resulting solution was stirred at ambient temperature for 16 h, partitioned between ether and aqueous ammonium chloride, washed with saturated brine, dried over MgSO4, and concentrated. Purification of the residue by silica gel chromatography using 3:1 hexane:ethyl acetate gave 172 mg (39%) of the desired compound as a colorless oil. 1H NMR (CDCl3) δ 0.91 (br t,3H), 1.27 (5,J=7 Hz,3H), 1.4 (m,4H), 1.86 (m,1H), 2.10 (m,1H), 3.10 (m,2H), 3.66 (ddd,J=13,8,6 Hz,1H), 3.81 (ddd,13,8,6 Hz,1H), 4.2 (m,2H), 5.39 (dd,J=10,5 Hz,1H), 7.15 (td,J=7,1 Hz,1H), 7.31 (td,J=7,1 Hz,1H), 7.47 (d,J=7 Hz,1H), 7.60 (d,J=7 Hz,1H), 9.81 (br s,1H).

後処理

  1. customrecooled to -78° C.
  2. temperatureto warm to 0° C.
  3. custompartitioned between ether and aqueous ammonium chloride
  4. washwashed with saturated brine
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated
  7. customPurification of the residue by silica gel chromatography

出典と根拠

ORDレコード
ord-91c66e58ba964a34a2f2b72d701485dc
出典データセット
uspto-grants-1991_02
特許番号
US04994477

反応ノート

読み込み中…