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

HRID 1477349Notes

Reaction equation

HRID 1477349 reaction equation
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

Participants

5

Reactant 3

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

Product 1

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

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

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]+.

Workup

  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

Sources & evidence

ORD record
ord-0e45dcb6cab64be5bac3e7ca2979786a
Source dataset
uspto-grants-2016_08
Patent number
US09403794B2

Reaction notes

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