Triisopropylsilyl trifluoromethanesulfonate → 9-Benzyl-3,6-bis(triisopropylsilyl)-9H-carbazole

HRID 2045148Notes

Reaction equation

HRID 2045148 reaction equation
[CH2:1]([N:8]1[C:20]2[CH:19]=[CH:18][C:17](Br)=[CH:16][C:15]=2[C:14]2[C:9]1=[CH:10][CH:11]=[C:12](Br)[CH:13]=2)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Li]C[CH2:25][CH2:26][CH3:27].[CH:28]([Si:31](OS(C(F)(F)F)(=O)=O)([CH:35]([CH3:37])[CH3:36])[CH:32]([CH3:34])[CH3:33])([CH3:30])[CH3:29]>C1COCC1>[CH2:1]([N:8]1[C:20]2[CH:19]=[CH:18][C:17]([Si:31]([CH:35]([CH3:37])[CH3:36])([CH:32]([CH3:34])[CH3:33])[CH:28]([CH3:30])[CH3:29])=[CH:16][C:15]=2[C:14]2[C:9]1=[CH:10][CH:11]=[C:12]([Si:31]([CH:32]([CH3:34])[CH3:33])([CH:26]([CH3:27])[CH3:25])[CH:28]([CH3:30])[CH3:29])[CH:13]=2)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 2724529Triisopropylsilyl trifluoromethanesulfonateHCID 2802035N-benzyl-3,6-dibromocarbazole2×HCID 178418339Butyllithium

Product 1

HCID 583898579-Benzyl-3,6-bis(triisopropylsilyl)-9H-carbazoleYield 35%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

A 2 L dry round bottom flask was charged with N-benzyl-3,6-dibromocarbazole 3 (49 g, 0.118 mol) and 1 L of dry THF was added. The mixture was stirred until N-benzyl-3,6-dibromocarbazole 3 was dissolved. The mixture was then cooled to −78° C. and 2.5 M n-BuLi in hexanes (104 ml, 0.26 mol) was added dropwise. The mixture was stirred at −78° C. for 15 min and triisopropylsilyl-trifluoromethyl sulfonate (66 ml, 0.26 mol) was added. The mixture was left to warm up to room temperature overnight. The mixture was then quenched with sat. NH4Cl, extracted with methyl-t-butyl ether, dried over Na2SO4, filtered, concentrated, and purified over a 330 g SiO2 column to yield 9-benzyl-3,6-bis-triisopropylsilanyl-9H-carbazole 4 23.0 g (35%) as a transparent oil.

Workup

  1. customA 2 L dry round bottom flask
  2. additionwas added
  3. dissolutionwas dissolved
  4. waitThe mixture was left
  5. temperatureto warm up to room temperature overnight
  6. customThe mixture was then quenched with sat. NH4Cl
  7. extractionextracted with methyl-t-butyl ether
  8. dry with materialdried over Na2SO4
  9. filtrationfiltered
  10. concentrationconcentrated
  11. custompurified over a 330 g SiO2 column

Sources & evidence

ORD record
ord-d993deaf22e548209744f1c5acd841c5
Source dataset
uspto-grants-2013_11
Patent number
US08586973B2

Reaction notes

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