4-Vinylpyridine → 4,4'-(9,9-Bis-n-decyl-2,7-fluorenediyldi-2,1-ethenediyl)bis-pyridine

HRID 342906Notes

Reaction equation

HRID 342906 reaction equation
Br[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][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH3:35])([CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH3:25])[C:4]=2[CH:3]=1.[C:36]1(C)[CH:41]=CC=C[C:37]=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.[CH:58]([C:60]1[CH:65]=[CH:64][N:63]=[CH:62][CH:61]=1)=[CH2:59].C([N:68]([CH2:71][CH3:72])[CH2:69][CH3:70])C>[Pd]>[CH2:26]([C:5]1([CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH3:25])[C:6]2[CH:7]=[C:8]([CH:59]=[CH:58][C:60]3[CH:65]=[CH:64][N:63]=[CH:62][CH:61]=3)[CH:9]=[CH:10][C:11]=2[C:12]2[C:4]1=[CH:3][C:2]([CH:37]=[CH:36][C:41]1[CH:70]=[CH:69][N:68]=[CH:71][CH:72]=1)=[CH:14][CH:13]=2)[CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH3:35]

Participants

6

Reactant 4

HCID 75024-VinylpyridineHCID 8471TriethylamineHCID 80271Tri-o-tolylphosphineHCID 36612112,7-Dibromo-9,9-didecylfluorene

Product 1

HCID 675756704,4'-(9,9-Bis-n-decyl-2,7-fluorenediyldi-2,1-ethenediyl)bis-pyridineYield 71.48%

Reagents, catalysts & solvents 1

HCID 23938PalladiumCatalyst

Conditions

Temperature
95 °C

Procedure

2,7-Dibromo-9,9-di-n-decyl-9H-fluorene (10.0 g, 16.5 mmol), tri-o-tolylphosphine (2.01 g, 6.6 mmol), degassed triethylamine (40 ml) and 4-vinylpyridine (5.35 ml, 49.62 mmol) was added to a single-necked round bottom flask under to nitrogen equipped with a magnetic stir bar and a reflux condenser. The palladium catalyst (0.19 g, 0.83 mmol) was added and the solution heated at 95° C. for 18 hours. The reaction mixture was cooled to room temperature and the solvent removed under reduced pressure. The residue was dissolved in methylene chloride, and the organic layer washed three times with equal volumes of water, dried over anhydrous MgSO4, filtered and concentrated. The product was purified by column chromotography on alumina using 30/70 ethyl acetate/hexane to yield the product as a yellow oil in 71.48% yield.Mass Spec. m/z 652 (M+), 511 (M--C10H21). Elemental Analysis: Calculated for C47H60N2 : C, 86.45, H, 9.26, N, 4.29. Found: C, 86.50, H, 8.84, N, 3.78.

Workup

  1. additionwas added to a single-necked round bottom flask under to nitrogen
  2. customequipped with a magnetic stir bar and a reflux condenser
  3. temperatureThe reaction mixture was cooled to room temperature
  4. customthe solvent removed under reduced pressure
  5. dissolutionThe residue was dissolved in methylene chloride
  6. washthe organic layer washed three times with equal volumes of water
  7. dry with materialdried over anhydrous MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe product was purified by column chromotography on alumina using 30/70 ethyl acetate/hexane

Sources & evidence

ORD record
ord-ed72695deaa241cba0ef112315c050f6
Source dataset
uspto-grants-1999_01
Patent number
US05859251

Reaction notes

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