Imidazole → 3'-Bromo-4'-t-butyldiphenylsilyloxymethyl-1,1'-biphenyl-2-nitrile

HRID 1379872Notes

Reaction equation

HRID 1379872 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([C:10]2[C:11]([C:16]#[N:17])=[CH:12][CH:13]=[CH:14][CH:15]=2)[CH:5]=[CH:6][C:7]=1[CH2:8][OH:9].N1C=CN=C1.[C:23]([Si:27](Cl)([C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1)[C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1)([CH3:26])([CH3:25])[CH3:24].O>CN(C)C=O>[Br:1][C:2]1[CH:3]=[C:4]([C:10]2[C:11]([C:16]#[N:17])=[CH:12][CH:13]=[CH:14][CH:15]=2)[CH:5]=[CH:6][C:7]=1[CH2:8][O:9][Si:27]([C:23]([CH3:26])([CH3:25])[CH3:24])([C:34]1[CH:35]=[CH:36][CH:37]=[CH:38][CH:39]=1)[C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1

Participants

6

Reactant 4

HCID 795ImidazoleHCID 962WaterHCID 94078tert-ButyldiphenylchlorosilaneHCID 701916703'-Bromo-4'-hydroxymethyl-1,1'-biphenyl-2-nitrile

Product 1

HCID 1317202193'-Bromo-4'-t-butyldiphenylsilyloxymethyl-1,1'-biphenyl-2-nitrileYield 100.2%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 670 mg (2.35 mmol) of 3'-bromo-4'-hydroxymethyl-1,1'-biphenyl-2-nitrile (Step F) in 5 mL of dry dimethylformamide under a nitrogen atmosphere was added 237 mg (3.49 mmol) of imidazole. The reaction mixture was cooled to 0° C. and 0.73 mL (2.8 mmol) of t-butylchlorodiphenylsilane was added dropwise by syringe over 5 minutes. The resulting solution was stirred at 0° C. for 15 minutes then at room temperature for 2 hours. The reaction mixture was poured into 100 mL of water and extracted with ether (3×75 mL). The combined ether extracts were washed with water (75 mL), saturated aqueous sodium bicarbonate (75 mL) and brine (75 mL). The organic layer was dried over magnesium sulfate, filtered and the solvent removed under vacuum to give an oil which was purified by flash column chromatography on silica gel, eluting with hexanes/ethyl acetate (9:1), to afford 1.24 g (100%) of the product as a clear oil. 1H NMR (200 MHz, CDCl3): δ 1.13 (s, 3H), 4.80 (s, 2H), 7.30-7.50 (m, 9H), 7.55-7.80 (m, 7H), 7.86 (d, 8 Hz, 1H). FAB-MS: calculated for C30H28BrNOSi 526; found 527, 528, 271 (60%).

Workup

  1. waitat room temperature for 2 hours
  2. extractionextracted with ether (3×75 mL)
  3. washThe combined ether extracts were washed with water (75 mL), saturated aqueous sodium bicarbonate (75 mL) and brine (75 mL)
  4. dry with materialThe organic layer was dried over magnesium sulfate
  5. filtrationfiltered
  6. customthe solvent removed under vacuum
  7. customto give an oil which
  8. customwas purified by flash column chromatography on silica gel
  9. washeluting with hexanes/ethyl acetate (9:1)

Sources & evidence

ORD record
ord-9a5b2643b3d0419ca0e0911c4e9362cb
Source dataset
uspto-grants-1997_09
Patent number
US05672596

Reaction notes

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