2-Bromothiophene → Fluorene

HRID 2209321Notes

Reaction equation

HRID 2209321 reaction equation
C(N1C2=CC3C(=CC2=C(C2SC(Br)=CC=2)C1=O)N(CCCCCC)C(=O)C=3C1SC(Br)=CC=1)CCCCC.CC1(C)C(C)(C)OB(C(CCCC)C[C:49]2[C:61]3[C:60](CC)(CC)[C:59]4[C:54](=[CH:55][CH:56]=[C:57](B5OC(C)(C)C(C)(C)O5)[CH:58]=4)[C:53]=3[CH:52]=[CH:51][CH:50]=2)O1.[O-]P([O-])([O-])=O.[K+].[K+].[K+].BrC1SC=CC=1>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].CO.C1(C)C=CC=CC=1.O>[CH:49]1[C:61]2[CH2:60][C:59]3[C:54](=[CH:55][CH:56]=[CH:57][CH:58]=3)[C:53]=2[CH:52]=[CH:51][CH:50]=1

Participants

9

Reactant 4

HCID 138512-BromothiopheneHCID 62657Potassium Phosphate, TribasicHCID 866982691,5-Dihexyl-3,7-di-(5-bromothiophen-2-yl)-1H,5H-pyrrolo[2,3-f]indole-2,6-dioneHCID 866982702,7-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-di-ethylhexylfluorene

Product 1

HCID 6853FluoreneYield 372%

Reagents, catalysts & solvents 4

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 887MethanolSolventHCID 1140TolueneSolventHCID 22272177Toluene waterSolvent

Procedure

A mixture of 1,5-Dihexyl-3,7-di-(5-bromothiophen-2-yl)-1H,5H-pyrrolo[2,3-f]indole-2,6-dione (0.150 g, 0.221 mmol), 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-di-ethylhexylfluorene (0.149 g, 0232 mmol), Pd2(dba)3 (5.0 mg), (o-tol)3P (3.0 mg), K3PO4 (0.187 g) and toluene/H2O (20 mL/1 mL) was heated at reflux for 24 h. 2-bromothiophene (0.035 g, 0.22 mmol) in toluene (1 mL) was added and the resulting mixture was stirred for another 12 h. Then, after cooling to room temperature, the mixture was dropped into methanol to precipitate. After being filtered and dried, the precipitation was Soxhlet extracted with methanol, acetone, hexane, dichloromethane and chloroform in succession. The chloroform solution was concentrated and reprecipitated in methanol. The solid was filtered and dried to yield polymer (0.165 g, 82.5%) as a blue-green solid.

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 24 h
  3. customto precipitate
  4. filtrationAfter being filtered
  5. customdried
  6. customthe precipitation
  7. extractionextracted with methanol, acetone, hexane, dichloromethane and chloroform in succession
  8. concentrationThe chloroform solution was concentrated
  9. customreprecipitated in methanol
  10. filtrationThe solid was filtered
  11. customdried

Sources & evidence

ORD record
ord-5217ef704d574976955f1011694a7d6a
Source dataset
uspto-grants-2016_06
Patent number
US09379335B2

Reaction notes

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