Diethyl Ether → 4-Ethynyl-α,α-diphenylbenzenemethanol

HRID 370301Notes

Reaction equation

HRID 370301 reaction equation
CCOCC.C[Si]([C:10]#[C:11][C:12]1[CH:25]=[CH:24][C:15]([C:16]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)=[O:17])=[CH:14][CH:13]=1)(C)C.[C:26]1([Li])[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1>O>[C:11]([C:12]1[CH:25]=[CH:24][C:15]([C:16]([C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[OH:17])=[CH:14][CH:13]=1)#[CH:10]

Participants

5

Reactant 3

HCID 3283Diethyl EtherHCID 15849413HCID 15849413, compoundHCID 178506676HCID 178506676, compound

Product 1

HCID 150125944-Ethynyl-α,α-diphenylbenzenemethanolYield 81%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Procedure

To a flask containing a mixture of 4-bromobenzophenone (1.31 g, 5.0 mmol). PdCl2 (PPh3)2 (70 mg. 0.10 mmol), and CuI (10 mg, 0.050 mmol) was added Et2NH (50 mL) and trimethylsilyl-acetylene (0.85 mL, 6.0 mmol) under a nitrogen atmosphere. The mixture was stirred at room temperature for 5 h. 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 to afford pale brown crystalline 4-(trimethylsilylethynyl)benzophenone in 93% yield (1.30 g). 1H NMR (300 MHz, C6D6, 25° C., TMS): δ=0.25 (s, 9 H, CH3) 7.44-7.74 (m 9 H, Ph and C6H4); MS (EI) : m/e 278 (M+ --CH3) To a Et2O solution (100 mL) of 4-(trimethylsilylethynyl)benzophenone (1.39 g, 5.0 mmol) prechilled to -30° C. was slowly added a solution of phenyllithium (3.33 mL, 6.0 mmol, 1.8 M in cyclohexane-ether). The solution was slowly warmed to room temperature and stirred for 4 hours. 1 mL of H2O was added and the solution was stirred for 30 minutes. Additional H2O (>200 mL) was added and the organic layer was collected, dried over MgSO4, filtered through Al2O3, and pumped dry. The residue was chromatographed using CH2Cl2 /hexane (2:1) as eluent to afford (4-ethynylphenyl)-diphenylmethanol as a pale yellow oil in 81% yield (1.24 g).

Workup

  1. customprechilled to -30° C.
  2. stirringthe solution was stirred for 30 minutes
  3. customthe organic layer was collected
  4. dry with materialdried over MgSO4
  5. filtrationfiltered through Al2O3
  6. custompumped dry
  7. customThe residue was chromatographed

Sources & evidence

ORD record
ord-eb263001995747b2a28b63bab7a37eb5
Source dataset
uspto-grants-2000_10
Patent number
US06140503

Reaction notes

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