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

HRID 2285333Notes

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-18317ab1cc5b49389ea67ebfacad0d38
Source dataset: uspto-grants-2015_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09147848B2

Reaction notes

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