Dimethylformamide → 9-(2-(2-methoxyethoxy)ethyl)-9H-carbazole-3-carbaldehyde

HRID 1749242ノート

反応式

HRID 1749242 の反応式
Br[C:2]1[CH:3]=[CH:4][C:5]2[N:6]([CH2:15][CH2:16][O:17][CH2:18][CH2:19][O:20][CH3:21])[C:7]3[C:12]([C:13]=2[CH:14]=1)=[CH:11][CH:10]=[CH:9][CH:8]=3.[Li]CCCC.CN([CH:30]=[O:31])C>C1COCC1>[CH3:21][O:20][CH2:19][CH2:18][O:17][CH2:16][CH2:15][N:6]1[C:5]2[CH:4]=[CH:3][C:2]([CH:30]=[O:31])=[CH:14][C:13]=2[C:12]2[C:7]1=[CH:8][CH:9]=[CH:10][CH:11]=2

参加物

5

反応物 3

HCID 6228DimethylformamideHCID 708962893-bromo-9-(2-(2-methoxyethoxy)ethyl)-9H-carbazoleHCID 178418339Butyllithium

生成物 1

HCID 866726799-(2-(2-methoxyethoxy)ethyl)-9H-carbazole-3-carbaldehyde収率 60%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
-78 °C

実験手順

To a solution of 2a (1.5 g, 4.3 mmol) in dried THF (45 mL) was added n-BuLi (3.5 mL 5.2 mmol) at −78° C. The resulting mixture was stirred at −78° C. for 1 h and then added with dried DMF (3 mL). The reaction mixture was allowed to warm to room temperature and stirred overnight before quenched with aqueous ammonia chloride solution. Water was added and extracted with ethyl acetate three times. The combined organic phase was washed with brine and dried over anhydrous sodium sulfate. After removing the solvent, the residue was purified by silica gel chromatography using ethyl acetate and petroleum ether (EA:PE=1:2) as eluent to afford 3a (0.76 g) as yellow solid in 60% yield. NMR (400 MHz, CDCl3) δ 10.07 (s, 1H), 8.58 (d, J=0.8 Hz, 1H), 8.13 (d, J=8.0 Hz, 1H), 7.98 (dd, J=8.8 Hz, 0.8 Hz, 1H), 7.51 (m, 3H), 7.30 (m, 1H), 4.53 (t, J=6.0 Hz, 2H), 3.87 (t, J=6.0 Hz, 2H), 3.49 (m, 2H), 3.38 (m, 2H), 3.26 (s, 3H). 13C NMR (400 MHz, CDCl3) δ 191.8, 144.3, 141.1, 128.5, 127.1, 126.6, 123.7, 123.0, 122.9, 120.6, 120.4, 109.4, 109.3, 71.8, 70.8, 69.1, 59.0, 43.4. MS (FAB) m/z Calcd for C18H19NO3 297.1. Found 297.3 [M]+.

後処理

  1. temperatureto warm to room temperature
  2. stirringstirred overnight
  3. custombefore quenched with aqueous ammonia chloride solution
  4. additionWater was added
  5. extractionextracted with ethyl acetate three times
  6. washThe combined organic phase was washed with brine
  7. dry with materialdried over anhydrous sodium sulfate
  8. customAfter removing the solvent
  9. customthe residue was purified by silica gel chromatography

出典と根拠

ORDレコード
ord-7942b241abf348368f26fe29ed4bd6b2
出典データセット
uspto-grants-2015_10
特許番号
US09156814B2

反応ノート

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