Diisopropylamine → Bis(4-((trimethylsilyl)ethynyl)phenyl)methanone

HRID 370298

Reaction equation

HRID 370298 reaction equation
Br[C:2]1[CH:16]=[CH:15][C:5]([C:6]([C:8]2[CH:13]=[CH:12][C:11](Br)=[CH:10][CH:9]=2)=[O:7])=[CH:4][CH:3]=1.N([CH:21]([CH3:23])C)C(C)C.[CH3:24][Si:25]([C:28]#[CH:29])([CH3:27])[CH3:26]>[Cu]I.C1COCC1>[CH3:24][Si:25]([C:28]#[C:29][C:2]1[CH:16]=[CH:15][C:5]([C:6]([C:8]2[CH:13]=[CH:12][C:11]([C:23]#[C:21][Si:25]([CH3:27])([CH3:26])[CH3:24])=[CH:10][CH:9]=2)=[O:7])=[CH:4][CH:3]=1)([CH3:27])[CH3:26]

Participants

6

Reactant 3

HCID 7912DiisopropylamineHCID 66111TrimethylsilylacetyleneHCID 728684,4'-Dibromobenzophenone

Product 1

HCID 10571474Bis(4-((trimethylsilyl)ethynyl)phenyl)methanoneYield 96%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8028TetrahydrofuranSolvent

Procedure

To a flask containing a mixture of 4,4'-dibromobenzophenone (5.0 g, 14.7 mmol), PdCl2 (PPh3)2 (0.42 mg, 0.60 mmol), and CuI (60 mg, 0.30 mmol) was added THF (100 mL), iPr2NH (20 mL) and trimethylsilylacetylene (4.6 mL, 32.5 mmol) under a nitrogen atmosphere. The mixture was stirred at room temperature for 40 hours. The solvent was removed under vacuum, and the residue was extracted with CH2Cl2 /H2O. The organic layer was collected, dried over MgSO4, filtered through Al2O3, and pumped dry. The residue was recrystallized from CH2Cl2 /hexane at -30° C. to afford pale brown crystalline 4,4'-bis(trimethylsilylethynyl)benzophenone in 96% yield (5.29 g). 1H NMR (300 MHz, C6D6, 25° C., TMS): δ=0.25 (s, 18 H, CH3), 7.53 (d, J=8.6 Hz, 4 H, C6H4), 7.69 (d, 4 H, C6H4). To a mixture of 4,4'-bis(trimethylsilylethynyl)benzophenone (1.0 g, 2.67 mmol) and KOH (0.30 g, 5.36 mmol) was added 50 mL of MeOH and the solution was stirred at room temperature for 3 hours. The solution was then extracted with Et2O. The Et2O solution was pumped dry and the residue was chromatographed using EtOAc/hexane (1:50 to 1:5) as eluent to afford 4,4'-diethynylbenzophenone in 68% yield (0.42 g).

Workup

  1. additionTo a flask containing
  2. customThe solvent was removed under vacuum
  3. extractionthe residue was extracted with CH2Cl2 /H2O
  4. customThe organic layer was collected
  5. dry with materialdried over MgSO4
  6. filtrationfiltered through Al2O3
  7. custompumped dry
  8. customThe residue was recrystallized from CH2Cl2 /hexane at -30° C.

Sources & evidence

ORD record
ord-f1d3f588ebea4db4bc66326f516dc6e7
Source dataset
uspto-grants-2000_10
Patent number
US06140503

Linked notes

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