Sodium Hydroxide → HCID 86674361, compound

HRID 2406420Notes

Reaction equation

HRID 2406420 reaction equation
[Br:1][C:2]1[CH:14]=[CH:13][C:12]2[C:11]3[C:6](=[CH:7][C:8]([Br:15])=[CH:9][CH:10]=3)[CH2:5][C:4]=2[CH:3]=1.[F:16][C:17]([F:47])([F:46])[C:18]([F:45])([F:44])[C:19]([F:43])([F:42])[C:20]([F:41])([F:40])[C:21]([F:39])([F:38])[C:22]([F:37])([F:36])[C:23]([F:35])([F:34])[C:24]([F:33])([F:32])[CH2:25][CH2:26][CH2:27][CH:28](I)[CH2:29][CH3:30].[OH-].[Na+]>C1(C)C=CC=CC=1.[N+](CCCC)(CCCC)(CCCC)CCCC.[Br-]>[Br:1][C:2]1[CH:14]=[CH:13][C:12]2[C:11]3[C:6](=[CH:7][C:8]([Br:15])=[CH:9][CH:10]=3)[C:5]([CH2:30][CH2:29][CH2:28][CH2:27][CH2:26][CH2:25][C:24]([F:32])([F:33])[C:23]([F:34])([F:35])[C:22]([F:36])([F:37])[C:21]([F:38])([F:39])[C:20]([F:40])([F:41])[C:19]([F:42])([F:43])[C:18]([F:44])([F:45])[C:17]([F:47])([F:46])[F:16])([CH2:30][CH2:29][CH2:28][CH2:27][CH2:26][CH2:25][C:24]([F:33])([F:32])[C:23]([F:35])([F:34])[C:22]([F:37])([F:36])[C:21]([F:39])([F:38])[C:20]([F:41])([F:40])[C:19]([F:43])([F:42])[C:18]([F:45])([F:44])[C:17]([F:47])([F:46])[F:16])[C:4]=2[CH:3]=1

Participants

6

Reactant 3

HCID 14798Sodium HydroxideHCID 1400732,7-DibromofluoreneHCID 86674362HCID 86674362, compound

Product 1

HCID 86674361HCID 86674361, compoundYield 72.1%

Reagents, catalysts & solvents 2

HCID 74236Tetrabutylammonium BromideCatalystHCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

To a magnetically stirred solution of 2,7-dibromofluorene 1 (2.00 g, 6.17 mmol) and semi-perfluoroalkyl iodide 4 (9.72 g, 15.4 mmol) in toluene (12 cm3) were added 50% (w/w) NaOH aqueous solution (24 g) and Bu4NBr (0.20 g, 0.62 mmol). The mixture was then heated to 80° C. After the reaction was stirred overnight under N2 atmosphere, it was allowed to cool to ambient temperature and quenched by the addition of water (150 cm3). The product was extracted with hexanes (150 cm3). The organic layer was then washed with water (150 cm3), dried over anhydrous MgSO4 and concentrated under reduced pressure. The crude product was purified by flash column chromatography (silica gel, hexanes) and then recrystallized from hexanes (40 cm3) twice to give the dibromofluorene 6 as colorless crystals (5.91 g, 72%); mp 82-83° C. (hexanes); (Found: C, 37.4; H, 2.1. C41H30Br2F34 requires C, 37.1; H, 2.3%); IR (KBr) νmax: 2932, 2855, 1600, 1448, 1371, 1329, 1245, 1208, 1150, 1054, 1017, 980, 954, 810, 705 cm−1; 1H NMR (500 MHz, CDCl3, δ) 7.55 (d, J=8 Hz, 2H, Ar—H), 7.49 (dd, J=1.5, 8 Hz, 2H, Ar—H), 7.46 (d, J=1.5 Hz, 2H, Ar—H), 2.00-1.90 (m, 8H, 2×ArCCH2 and 2×CH2CF2), 1.47-1.41 (m, 4H, 2×CH2CH2CF2), 1.20-1.09 (m, 8H, 2×ArCCH2CH2CH2 and 2×CH2CH2CH2CF2), 0.65-0.59 ppm (m, 4H, 2×ArCCH2CH2); 13C NMR (126 MHz, CDCl3, δ) 152.1, 139.1, 130.3, 126.0, 121.6, 121.2, 55.5, 40.0, 30.7 (t, J=22 Hz), 29.4, 28.7, 23.5, 20.0 ppm; m/z (ESI) 1328.0 [M+. C4H30Br2F34: requires M, 1328.01].

Workup

  1. temperatureto cool to ambient temperature
  2. customquenched by the addition of water (150 cm3)
  3. extractionThe product was extracted with hexanes (150 cm3)
  4. washThe organic layer was then washed with water (150 cm3)
  5. dry with materialdried over anhydrous MgSO4
  6. concentrationconcentrated under reduced pressure
  7. customThe crude product was purified by flash column chromatography (silica gel, hexanes)
  8. customrecrystallized from hexanes (40 cm3) twice

Sources & evidence

ORD record
ord-3e9c0b5e9a8b49689fdc69d7b2eb72f7
Source dataset
uspto-grants-2014_08
Patent number
US08809111B2

Reaction notes

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