Tetrahydrofuran → Tri(4-(trimethylsilylethynyl)phenyl)methanol

HRID 370302

Reaction equation

HRID 370302 reaction equation
[Li]CCCC.Br[C:7]1[CH:12]=[CH:11][C:10]([C:13]#[C:14][Si:15]([CH3:18])([CH3:17])[CH3:16])=[CH:9][CH:8]=1.C1COCC1.[CH3:24][Si:25]([C:28]#[C:29][C:30]1[CH:49]=[CH:48][C:33]([C:34]([C:36]2[CH:41]=[CH:40][C:39]([C:42]#[C:43][Si:44]([CH3:47])([CH3:46])[CH3:45])=[CH:38][CH:37]=2)=[O:35])=[CH:32][CH:31]=1)([CH3:27])[CH3:26]>CCOCC.O>[CH3:16][Si:15]([C:14]#[C:13][C:10]1[CH:11]=[CH:12][C:7]([C:34]([C:33]2[CH:32]=[CH:31][C:30]([C:29]#[C:28][Si:25]([CH3:24])([CH3:26])[CH3:27])=[CH:49][CH:48]=2)([C:36]2[CH:37]=[CH:38][C:39]([C:42]#[C:43][Si:44]([CH3:47])([CH3:46])[CH3:45])=[CH:40][CH:41]=2)[OH:35])=[CH:8][CH:9]=1)([CH3:18])[CH3:17]

Participants

7

Reactant 4

HCID 8028TetrahydrofuranHCID 4226980(4-Bromophenylethynyl)trimethylsilaneHCID 10571474Bis(4-((trimethylsilyl)ethynyl)phenyl)methanoneHCID 178418339Butyllithium

Product 1

HCID 15849416Tri(4-(trimethylsilylethynyl)phenyl)methanolYield 77%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 3283Diethyl EtherSolvent

Conditions

Temperature
-30 °C

Procedure

A solution of n-BuLi (2.1 mL, 3.36 mmol, 1.6 M in hexane) was added to a solution of (4-bromophenylethynyl)trimethylsilane (0.69 mg, 2.74 mmol) in 50 mL of Et2O prechilled to -78° C. The solution was then stirred at -30° C. for 15 minutes. The solution was warmed to room temperature, stirred for 1 hour, and cooled to -30° C. A THF solution (20 mL) of 4,4'-bis(trimethylsilylethynyl)benzophenone (0.83 g, 2.19 nmol) prechilled to -30° C. was added slowly and the resulting mixture was stirred for 15 minutes. The solution was warmed to 0° C. and stirred for 2 hours. After addition of 1 mL of H2O the solution was pumped dry. The residue was chromatographed using CH2Cl2 /hexane (1:5 to 2:1) as eluent to afford tri(4-(trimethylsilylethynyl)phenyl)methanol as a colorless powder in 77% yield (0.92 q). 1H NMR (300 MHz, CDCL3, 25° C., TMS): 0.22 (s, 27 H, CH3), 2.72 (s, 1 h, OH), 7.13 (d, J=8.4 Hz, 6 H, C6H4), 7.38 (d, 6 H, C6H4). To a mixture of tri (4-(trimethylsilylethynyl)phenyl)methanol (0.92 g, 1.68 mmol) and KOH (0.28 g, 5.0 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 solution was pumped dry and the residue was chromatographed using EtOAc/hexane (1:50 to 1:5) as eluent to afford tri(4-ethynylphenyl)methanol as a colorless powder in 84% yield (0.47 g). Anal. Calcd for C34H40Si3O: C 74.39, H 7.34. Found: C 74.03, H 7.28. 1H NMR (300 MHz, CDCl3, 25° C., TMS) : 2.73 (s, 1 H, OH), 3.06 (s, 3 H, ≡CH), 7.19 (d, J=8.2 Hz, 6 H, C6H4), 7.43 (d, 6 H, C6H4) ; IR (KBr, cm-1): 1018 (m, C--O), 2107 (w, C≡C); 3554 (m, O--H).

Workup

  1. customprechilled to -78° C
  2. temperatureThe solution was warmed to room temperature
  3. stirringstirred for 1 hour
  4. temperaturecooled to -30° C
  5. customprechilled to -30° C.
  6. additionwas added slowly
  7. stirringthe resulting mixture was stirred for 15 minutes
  8. temperatureThe solution was warmed to 0° C.
  9. stirringstirred for 2 hours
  10. customwas pumped dry
  11. customThe residue was chromatographed

Sources & evidence

ORD record
ord-0eeeb9d8c81d4b2d8bff817c8d45b86d
Source dataset
uspto-grants-2000_10
Patent number
US06140503

Linked notes

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