Imidazole → 3-((Tert-butyldimethylsilyl)oxy)aniline

HRID 1753658Notes

Reaction equation

HRID 1753658 reaction equation
[NH2:1][C:2]1[CH:3]=[C:4]([OH:8])[CH:5]=[CH:6][CH:7]=1.N1C=CN=C1.[CH3:14][C:15]([Si:18](Cl)([CH3:20])[CH3:19])([CH3:17])[CH3:16]>CN(C=O)C>[Si:18]([O:8][C:4]1[CH:3]=[C:2]([CH:7]=[CH:6][CH:5]=1)[NH2:1])([C:15]([CH3:17])([CH3:16])[CH3:14])([CH3:20])[CH3:19]

Participants

5

Reactant 3

HCID 795ImidazoleHCID 115683-AminophenolHCID 28928tert-Butyldimethylsilyl chloride

Product 1

HCID 143147823-((Tert-butyldimethylsilyl)oxy)anilineYield 76.3%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

3-Aminophenol (21.8 g, 0.200 mol) and imidazole (34 g, 0.50 mol) were dissolved in DMF (200 mL), the solution was cooled with an ice-water bath, and TBDMSCl (36.1 g, 0.24 mol) was added in one portion. The cooling bath was removed, the reaction mixture was allowed to warm-up to room temperature, and stirred for 1 h. DMF (ca. 150 mL) was evaporated in vacuo at +55° C., the residue was diluted with AcOEt (250 mL), washed with sat. aq. NaHCO3 (twice), water (several times), brine and dried over MgSO4. After evaporation of solvents, the oily residue was dried in vacuo (0.5 Torr) to a constant weight. Purification by column chromatography (gradient elution with hexane to hexane/ether=5/1) afforded compound 2 (Rf=0.24 in hexane/ether=8/1) as a clear oil (34.1 g, 76%). 1H NMR (300 MHz, CDCl3): δ=0.21 (s, 6 H, SiMe2But), 0.99 (s, 9 H, SiMe2But), 3.60 (br. s, 2 H, NH2), 6.18 (m, 1 H), 6.28 (m, 2 H), 6.98 (m, 1 H) ppm.

Workup

  1. temperaturethe solution was cooled with an ice-water bath
  2. customThe cooling bath was removed
  3. customDMF (ca. 150 mL) was evaporated in vacuo at +55° C.
  4. additionthe residue was diluted with AcOEt (250 mL)
  5. washwashed with sat. aq. NaHCO3 (twice), water (several times), brine
  6. dry with materialdried over MgSO4
  7. customAfter evaporation of solvents
  8. customthe oily residue was dried in vacuo (0.5 Torr) to a constant weight
  9. customPurification
  10. washby column chromatography (gradient elution with hexane to hexane/ether=5/1)

Sources & evidence

ORD record
ord-c4fc0ea3dca148cda8ff305482966777
Source dataset
uspto-grants-2015_10
Patent number
US09164086B2

Reaction notes

Loading…