2-(Tri-n-butylstannyl)thiophene → 2,7-bis-(2-thienyl)-9,9-di-(n-decyl)-9H-fluorene

HRID 342904Notes

Reaction equation

HRID 342904 reaction equation
C([Sn](CCCC)(CCCC)[C:6]1[S:7][CH:8]=[CH:9][CH:10]=1)CCC.Br[C:20]1[CH:32]=[CH:31][C:30]2[C:29]3[C:24](=[CH:25][C:26](Br)=[CH:27][CH:28]=3)[C:23]([CH2:44][CH2:45][CH2:46][CH2:47][CH2:48][CH2:49][CH2:50][CH2:51][CH2:52][CH3:53])([CH2:34][CH2:35][CH2:36][CH2:37][CH2:38][CH2:39][CH2:40][CH2:41][CH2:42][CH3:43])[C:22]=2[CH:21]=1>C1(C)C=CC=CC=1.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>[S:7]1[CH:8]=[CH:9][CH:10]=[C:6]1[C:26]1[CH:27]=[CH:28][C:29]2[C:30]3[C:22](=[CH:21][C:20]([C:6]4[S:7][CH:8]=[CH:9][CH:10]=4)=[CH:32][CH:31]=3)[C:23]([CH2:34][CH2:35][CH2:36][CH2:37][CH2:38][CH2:39][CH2:40][CH2:41][CH2:42][CH3:43])([CH2:44][CH2:45][CH2:46][CH2:47][CH2:48][CH2:49][CH2:50][CH2:51][CH2:52][CH3:53])[C:24]=2[CH:25]=1

Participants

5

Reactant 2

HCID 27793732-(Tri-n-butylstannyl)thiopheneHCID 36612112,7-Dibromo-9,9-didecylfluorene

Product 1

HCID 154044302,7-bis-(2-thienyl)-9,9-di-(n-decyl)-9H-fluoreneYield 70%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolvent

Procedure

2-(tributylstannyl)thiophene (5.80 ml, 0.018 mol) was added under nitrogen directly to a single-necked round bottom flask equipped with a condenser and a magnetic stir bar that had been previously dried in an oven at 110° C. The 2,7-dibromo-9,9-di-n-decyl-9H-fluorene (5.26 g, 8.70 mmol) was weighed into a beaker and dissolved in toluene (14 ml) which had been freshly distilled and degassed with nitrogen. The resulting fluorene solution was pipetted into the round bottom flask and the beaker rinsed twice with 3 ml portions of degassed toluene. Pd(PPh3)4 (0.50 g, 0.43 mmol) and PdCl2 (PPh3)2 (0.31 g, 0.44 mmol) were added to the reaction flask and the solution refluxed until it turned black. The toluene was removed under reduced pressure and the residue dissolved in hexane. The hexane solution was stirred vigorously with a 100 ml of a 2% aqueous KF solution for 3 hours. The organic layer was separated, washed twice with an equal volume of water, dried over anhydrous MgSO4, filtered and concentrated. The crude product was purified by column chromotography on silica gel using hexane as the eluent. The purified waxy solid compound (mp 59.9°-60.8° C.) was isolated in a 70% yield. Mass Spec. m/z 610 (M+), 469 (M--C10H21), Elemental Analysis: Calculated for C41H52S2 : C, 80.60, H, 8.91, S, 10.49. Found: C, 80.55, H, 8.97, S, 10.08.

Workup

  1. customequipped with a condenser and a magnetic stir bar that
  2. customhad been previously dried in an oven at 110° C
  3. distillationhad been freshly distilled
  4. customdegassed with nitrogen
  5. washthe beaker rinsed twice with 3 ml portions of degassed toluene
  6. temperaturethe solution refluxed until it
  7. customThe toluene was removed under reduced pressure
  8. dissolutionthe residue dissolved in hexane
  9. customThe organic layer was separated
  10. washwashed twice with an equal volume of water
  11. dry with materialdried over anhydrous MgSO4
  12. filtrationfiltered
  13. concentrationconcentrated
  14. customThe crude product was purified by column chromotography on silica gel

Sources & evidence

ORD record
ord-f07768b789294631bbfd33461848a8ad
Source dataset
uspto-grants-1999_01
Patent number
US05859251

Reaction notes

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