Potassium Iodide → 2,7-Dibromo-9,9-dibutyl-9H-fluorene

HRID 873497Notes

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.Br[CH2:17][CH2:18][CH2:19][CH3:20].[OH-].[K+].[I-].[K+]>C1OCCOCCOCCOCCOCCOC1.O.CN(C=O)C>[CH2:17]([C:5]1([CH2:14][CH2:2][CH2:3][CH3:4])[C:4]2[CH:3]=[C:2]([Br:1])[CH:14]=[CH:13][C:12]=2[C:11]2[C:6]1=[CH:7][C:8]([Br:15])=[CH:9][CH:10]=2)[CH2:18][CH2:19][CH3:20]

Participants

Conditions

Temperature: 90 °C

Procedure

A mixture of 12.0 g (37 mmol) of 2,7-dibromofluorene 2-7, 12 mL (111 mmol) of 1-bromobutane, 6.3 g (1 mmol) of potassium hydroxide, 0.9 g (6 mmol) of potassium iodide, 0.29 g (1 mmol) of 18-crown-6 and 120 mL of DMF was stirred and heated to 90° C. for overnight under N2. After cooling to room temperature, the solution was poured to cold water and extracted with dichloromethane (3×50 mL). The combined organic layer was washed with water, dried over anhydrous NaSO4, filtered and evaporated to dryness. The crude product was purified by silica gel column chromatography using petroleum ether as eluent affording the desired product as a white solid (12.9 g, 80%). Mp: 116.8-118.5° C. 1H NMR (400 MHz, CDCl3, δ) 7.53 (d, J=8.8 Hz, 2H), 7.46 (dd, J=7.2 Hz, J=2.2 Hz, 4H), 1.90-1.94 (m, 4H), 1.06-1.11 (m, 4H), 0.70 (t, J=7.4 Hz, 3H), 0.54-0.59 (m, 4H). 13C NMR (100 MHz, CDCl3, δ) 152.5, 139.1, 130.2, 126.2, 121.5, 121.2, 55.6, 40.1, 25.8, 22.9, 13.8. MS (FAB) m/z 436.1 (M+).

Workup

temperatureAfter cooling to room temperature
extractionextracted with dichloromethane (3×50 mL)
washThe combined organic layer was washed with water
dry with materialdried over anhydrous NaSO4
filtrationfiltered
customevaporated to dryness
customThe crude product was purified by silica gel column chromatography

Sources & evidence

ORD record: ord-9bd15d22e07f4cc18b9a4b1ebd09d28b
Source dataset: uspto-grants-2015_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08975419B2

Reaction notes

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