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

HRID 1774085Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1774085
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

Komponenten

5

Edukt 3

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

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
-78 °C

Versuchsvorschrift

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]+.

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-ec0d483148ea43b89aaf03877bd99c6f
Quelldatensatz
uspto-grants-2016_02
Patentnummer
US09255933B2

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