Dimethylformamide → 3-(1-Adamantyl)-4-(t-butyldimethylsilyloxy)bromobenzene

HRID 860577Notes

Reaction equation

HRID 860577 reaction equation
[C:1]12([C:11]3[CH:16]=[C:15]([Br:17])[CH:14]=[CH:13][C:12]=3[OH:18])[CH2:10][CH:5]3[CH2:6][CH:7]([CH2:9][CH:3]([CH2:4]3)[CH2:2]1)[CH2:8]2.CN(C=O)C.C(N(CC)CC)C.[Si:31](Cl)([C:34]([CH3:37])([CH3:36])[CH3:35])([CH3:33])[CH3:32]>CN(C1C=CN=CC=1)C.O>[C:1]12([C:11]3[CH:16]=[C:15]([Br:17])[CH:14]=[CH:13][C:12]=3[O:18][Si:31]([C:34]([CH3:37])([CH3:36])[CH3:35])([CH3:33])[CH3:32])[CH2:2][CH:3]3[CH2:9][CH:7]([CH2:6][CH:5]([CH2:4]3)[CH2:10]1)[CH2:8]2

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 8471TriethylamineHCID 28928tert-Butyldimethylsilyl chlorideHCID 46704942-(1-Adamantyl)-4-bromophenol

Product 1

HCID 107883163-(1-Adamantyl)-4-(t-butyldimethylsilyloxy)bromobenzeneYield 64,152.199%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 962WaterSolvent

Procedure

A 2.0 L three-neck flask attached with a power-stirrer was charged with 2-adamantan-1-yl-4-bromophenol (102.8 g, 0.334 mol, 1.0 eq), DMAP (3.67 g, 0.0301 mol), anhydrous DMF (1.0 L) and triethylamine (76.1 g, 0.753 mol, 1.25 eq). Stirring was initiated and to the resulting solution at room temperature was added t-butyl-dimethylsilyl chloride (99.8 g, 0.662 mmol, 1.10 eq). The resulting mixture was allowed to stir overnight, poured into water, and extracted with diethyl ether (2×). The combined organics were washed successively with water and brine, dried over anhydrous magnesium sulfate, filtered, and evaporated. The residue was purified on silica gel (hexane) to give 179 g (70%) of 3-adamantan-1-yl-4-t-butyldimethylsilanyloxybromobenzene as a white powder. 1H NMR (300 MHz; CDCl3): δ 0.33 (s, 6H), 1.03 (s, 9H), 1.75 (brs, 6H), 2.06 (s, 9H), 6.65 (d, J=8.4 Hz, 1H), 7.14 (dd, J1=8.4 Hz, J2=2.1 Hz, 1H), 7.29 (d, J=2.1 Hz, 1H).

Workup

  1. customA 2.0 L three-neck flask attached with a power-stirrer
  2. customwas initiated and to the resulting solution at room temperature
  3. stirringto stir overnight
  4. extractionextracted with diethyl ether (2×)
  5. washThe combined organics were washed successively with water and brine
  6. dry with materialdried over anhydrous magnesium sulfate
  7. filtrationfiltered
  8. customevaporated
  9. customThe residue was purified on silica gel (hexane)

Sources & evidence

ORD record
ord-be20a6e71cb040c8a52d8870840d77da
Source dataset
uspto-grants-2006_12
Patent number
US07153875B2

Reaction notes

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