Sodium Carbonate → Tetraphenylenedione fluorene

HRID 1257982Notes

Reaction equation

HRID 1257982 reaction equation
Br[C:2]1[C:25]2[C:24]3[C:19](=[CH:20][CH:21]=[CH:22][CH:23]=3)[C:18]3[C:13](=[CH:14][CH:15]=[CH:16][CH:17]=3)[C:12]3[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=3)[C:6]=2[C:5](=[O:26])[C:4](=[O:27])[C:3]=1Br.C([C:37]1(CCCCCCCC)[C:49]2[CH:48]=[C:47](B3OC(C)(C)C(C)(C)O3)[CH:46]=[CH:45][C:44]=2[C:43]2[C:38]1=[CH:39][C:40](B1OC(C)(C)C(C)(C)O1)=[CH:41][CH:42]=2)CCCCCCC.C(=O)([O-])[O-].[Na+].[Na+]>CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)C.[Cl-].C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CO>[C:5]1(=[O:26])[C:6]2[C:7]3[C:12](=[CH:11][CH:10]=[CH:9][CH:8]=3)[C:13]3[C:18](=[CH:17][CH:16]=[CH:15][CH:14]=3)[C:19]3[C:24](=[CH:23][CH:22]=[CH:21][CH:20]=3)[C:25]=2[CH:2]=[CH:3][C:4]1=[O:27].[CH:39]1[C:38]2[CH2:37][C:49]3[C:44](=[CH:45][CH:46]=[CH:47][CH:48]=3)[C:43]=2[CH:42]=[CH:41][CH:40]=1

Participants

7

Reactant 3

HCID 10340Sodium CarbonateHCID 219820749,9-Dioctylfluorene-2,7-diboronic acid bis(pinacol) esterHCID 178515287HCID 178515287, compound

Product 1

HCID 86627079Tetraphenylenedione fluoreneYield 45%

Reagents, catalysts & solvents 3

HCID 21218Trioctylmethylammonium chlorideCatalystHCID 178418397HCID 178418397, compoundCatalystHCID 887MethanolSolvent

Procedure

A mixture of compound 9 (150.0 mg, 0.173 mmol), 2,2′-(9,9-dioctyl-9H-fluorene-2,7-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (131.0 mg, 0.173 mmol), and Aliquat 336 (0.02 g) was degassed 3 times with N2 before 3.0 mL of dry toluene was added. Tetrakis(triphenylphosphine)palladium (10 mg, 0.005 mmol) in an aqueous sodium carbonate solution (0.6 mL, 2M, deaerated for 2 hours) was added under N2. The mixture was stirred vigorously and heated at the refluxing temperature for 2 days. The highly viscous reaction mixture was poured into a boiling methanol (30 mL) to precipitate an orange polymer. The polymer was collected by filtration and washed with acetone, methanol, water, and dried under vacuum at 60° C. overnight. The polymer was dissolved in THF (170 mg in 9 mL of THF) and reprecipitated with 40 mL of acetone twice to give 140 mg of TPDKF as an orange polymer (45%); and Elemental analysis: C, 87.30; H, 9.57; O, 2.58.

Workup

  1. customwas degassed 3 times with N2 before 3.0 mL of dry toluene
  2. additionwas added
  3. temperatureheated at the refluxing temperature for 2 days
  4. customto precipitate an orange polymer
  5. filtrationThe polymer was collected by filtration
  6. washwashed with acetone, methanol, water
  7. customdried under vacuum at 60° C. overnight
  8. dissolutionThe polymer was dissolved in THF (170 mg in 9 mL of THF)
  9. customreprecipitated with 40 mL of acetone twice

Sources & evidence

ORD record
ord-39347dbd6beb4aa9ad21ed42c5dc49e0
Source dataset
uspto-grants-2013_06
Patent number
USRE044304E1

Reaction notes

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