Dimethylformamide → HCID 86761886, compound

HRID 1261870Notes

Reaction equation

HRID 1261870 reaction equation
[Br:1][C:2]1[CH:14]=[CH:13][C:12]2[C:11]3[C:6](=[CH:7][C:8](Br)=[CH:9][CH:10]=3)[C:5]([CH2:26][CH2:27][CH:28]([CH3:35])[CH2:29][CH2:30][CH2:31][CH:32]([CH3:34])[CH3:33])([CH2:16][CH2:17][CH:18]([CH3:25])[CH2:19][CH2:20][CH2:21][CH:22]([CH3:24])[CH3:23])[C:4]=2[CH:3]=1.[Li]CCCC.CCCCCC.CN(C)[CH:49]=[O:50]>C1COCC1.O.C1(C)C=CC=CC=1>[Br:1][C:2]1[CH:3]=[C:4]2[C:12]([C:11]3[CH:10]=[CH:9][C:8]([CH:49]=[O:50])=[CH:7][C:6]=3[C:5]2([CH2:16][CH2:17][CH:18]([CH3:25])[CH2:19][CH2:20][CH2:21][CH:22]([CH3:24])[CH3:23])[CH2:26][CH2:27][CH:28]([CH3:35])[CH2:29][CH2:30][CH2:31][CH:32]([CH3:33])[CH3:34])=[CH:13][CH:14]=1

Participants

8

Reactant 4

HCID 6228DimethylformamideHCID 8058HexaneHCID 11490379HCID 11490379, compoundHCID 178418339Butyllithium

Product 1

HCID 86761886HCID 86761886, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

To a flame-dried 3-neck round-bottomed flask equipped with a mechanical stirrer and an addition funnel was added 2,7-dibromo-9,9-bis(3,7-dimethyloctyl)fluorene (Example 6; 79.3 g, 131.2 mmol) and THF (350 mL) by cannula. The solution was cooled to −78° C. and 2.5 M n-BuLi in hexane (52.5 mL, 131.2 mmol) was added by addition funnel over 15 min. After stirring for 30 min, N,N-dimethylformamide (DMF, 20.0 mL, 262 mmol) in THF (30 mL) was added dropwise, and the reaction mixture was allowed to warm to room temperature overnight. Toluene and water were added, and the organic phase was further washed with water, dried with MgSO4, and concentrated. The crude product was purified by column chromatography eluting with heptane to 20% toluene/heptane to give 54 g (75%). 1H NMR (400 MHz, CDCl3) δ: 10.06 (s, 1H), 7.88-7.79 (m, 3H), 7.63 (m, 1H), 7.51 (m, 2H), 1.41 (m, 2H), 1.20-0.93 (m, 12H), 0.92-0.75 (m, 14H), 0.66 (m, 6H), 0.60-0.30 (m, 4H). Mass Spec. m/z 552, 554 (M+). Anal. Calcd. for C34H49BrO: C, 73.76%; H, 8.92%; Br, 14.43%. Found: C, 73.80%; H, 8.86%; Br, 14.64%.

Workup

  1. customTo a flame-dried 3-neck round-bottomed flask equipped with a mechanical stirrer and an addition funnel
  2. temperatureto warm to room temperature overnight
  3. washthe organic phase was further washed with water
  4. dry with materialdried with MgSO4
  5. concentrationconcentrated
  6. customThe crude product was purified by column chromatography
  7. washeluting with heptane to 20% toluene/heptane
  8. customto give 54 g (75%)

Sources & evidence

ORD record
ord-120e669449ec47be859eaee7f888530d
Source dataset
uspto-grants-2013_06
Patent number
US08471035B1

Reaction notes

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