N-Fluorobenzenesulfonimide → 3-fluoro-9-(2-(2-methoxyethoxy)ethyl)-9H-carbazole

HRID 1774085ノート

反応式

HRID 1774085 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.C1C=CC(S(N(S(C2C=CC=CC=2)(=O)=O)[F:37])(=O)=O)=CC=1>C1COCC1>[F:37][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

参加物

5

反応物 3

HCID 588007N-FluorobenzenesulfonimideHCID 708962893-bromo-9-(2-(2-methoxyethoxy)ethyl)-9H-carbazoleHCID 178418339Butyllithium

生成物 1

HCID 867279583-fluoro-9-(2-(2-methoxyethoxy)ethyl)-9H-carbazole収率 75%

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 3-bromo-9-(2-(2-methoxyethoxy)ethyl)-9H-carbazole (3.23 g, 9.3 mmol) in dry THF (50 ml) was added n-BuLi (1.6 M, 8.7 ml, 13.9 mmol) at −78° C. The resulting mixture was stirred for 50 min at −78° C. and then added with N-fluorobenzenesulfonimide (5.6 g, 18.6 mmol). The reaction mixture was allowed to warm to rt and stirred for 2 h before quenched with ammonia chloride solution. The organic layer was separated, dried over anhydrous sodium sulfate and evaporated under vacuum. The residue was purified by silica gel column chromatography eluting with 3:1 petroleum ether/ethyl acetate to give compound 5 in 75% yield. 1H NMR (400 MHz, CDCl3) δ 8.03 (d, J=7.6 Hz, 1H), 7.73 (dd, J=2.4 Hz, J=8.8 Hz 1H), 7.50-7.44 (m, 2H), 7.39 (dd, J=4.4 Hz, J=8.8 Hz, 1H), 7.25-7.17 (m, 2H), 4.49 (t, J=6.4 Hz, 2H), 3.86 (t, J=6.4 Hz, 2H), 3.52-3.50 (m, 2H), 3.43-3.41 (m, 2H), 3.32 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 158.6, 156.2, 141.4, 137.1, 126.3, 123.4, 123.3, 122.6, 122.6, 120.6, 119.1, 113.6, 113.3, 109.7, 109.6, 109.2, 106.1, 105.9, 72.1, 71.0, 69.4, 59.2, 43.4. HRMS (MALDI-TOF) m/z Calcd for C17H18FNO2 287.1316 Found 287.1314[M]+.

後処理

  1. temperatureto warm to rt
  2. stirringstirred for 2 h
  3. custombefore quenched with ammonia chloride solution
  4. customThe organic layer was separated
  5. dry with materialdried over anhydrous sodium sulfate
  6. customevaporated under vacuum
  7. customThe residue was purified by silica gel column chromatography
  8. washeluting with 3:1 petroleum ether/ethyl acetate

出典と根拠

ORDレコード
ord-ec0d483148ea43b89aaf03877bd99c6f
出典データセット
uspto-grants-2016_02
特許番号
US09255933B2

反応ノート

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