Potassium Carbonate → HCID 22723477, compound

HRID 1268491Notes

Reaction equation

HRID 1268491 reaction equation
[Br:1][C:2]1[CH:14]=[CH:13][C:12]2[C:11]3[C:6](=[CH:7][C:8](I)=[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([NH:42][C:43]2[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=2)[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=1.C(=O)([O-])[O-].[K+].[K+].COCCOCCN(CCOCCOC)CCOCCOC>[Cu]>[Br:1][C:2]1[CH:3]=[C:4]2[C:12]([C:11]3[CH:10]=[CH:9][C:8]([N:42]([C:43]4[CH:44]=[CH:45][CH:46]=[CH:47][CH:48]=4)[C:36]4[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=4)=[CH:7][C:6]=3[C:5]2([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])=[CH:13][CH:14]=1

Participants

6

Reactant 4

HCID 11430Potassium CarbonateHCID 11487DiphenylamineHCID 112414Ethanamine, 2-(2-methoxyethoxy)-N,N-bis[2-(2-methoxyethoxy)ethyl]-HCID 227234762-Bromo-9,9-didecyl-7-iodo-9H-fluorene

Product 1

HCID 22723477HCID 22723477, compoundYield 61%

Reagents, catalysts & solvents 1

HCID 23978CopperCatalyst

Procedure

A mixture of 2-bromo-7-iodo-9,9-didecylfluorene (52.13 g, 0.08 mol), diphenylamine (15.6 g, 0.0922 mol, 1.152 eq), potassium carbonate (25.5 g, 0.1844 mol), tris(2-(2-methoxyethoxy)ethyl)amine (TDA-1, 5 mL), copper bronze (3.0 g, 0.05 g atom) and xylenes (75 mL) was brought to reflux, and 35 mL, of xylenes were distilled off to reach a reaction temperature of 160° C. The reaction was maintained at this temperature for 18 hours. Some more solvent was distilled off to reach a reaction temperature of 175° C., where the reaction was held for additional 6 hours. The mixture was then cooled, diluted with 100 mL toluene, filtered, the filtrate was concentrated, and the residue was transferred to a column of 600 g of silica gel. Elution with 750 mL hexanes returned a mixture of dibromo and bromoiodo fluorenes as an oil, 10.3 g Elution with heptane-toluene, 1:1, gave the product, 33.48 g (61 % yield, 77% yield on consumed bromoiodo fluorene), m.p. 66.8-69.2° C. Mass Spec: 691, 693 (M+).

Workup

  1. temperatureto reflux
  2. distillation35 mL, of xylenes were distilled off
  3. customa reaction temperature of 160° C
  4. temperatureThe reaction was maintained at this temperature for 18 hours
  5. distillationSome more solvent was distilled off
  6. customa reaction temperature of 175° C., where
  7. temperatureThe mixture was then cooled
  8. additiondiluted with 100 mL toluene
  9. filtrationfiltered
  10. concentrationthe filtrate was concentrated
  11. washElution with 750 mL hexanes
  12. additiona mixture of dibromo and bromoiodo fluorenes as an oil, 10.3 g Elution with heptane-toluene, 1:1
  13. customgave
  14. customthe product, 33.48 g (61 % yield, 77% yield on consumed bromoiodo fluorene), m.p. 66.8-69.2° C

Sources & evidence

ORD record
ord-b66336f344e3485980f163c905cea772
Source dataset
uspto-grants-2003_04
Patent number
US06555682B1

Reaction notes

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