Imidazole → 4-(Tert-butyldimethylsilyl)oxy-2-nitroaniline

HRID 1839433Notes

Reaction equation

HRID 1839433 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([OH:8])=[CH:4][C:3]=1[N+:9]([O-:11])=[O:10].CN(C=O)C.N1C=CN=C1.[Si:22](Cl)([C:25]([CH3:28])([CH3:27])[CH3:26])([CH3:24])[CH3:23]>CCOC(C)=O>[N+:9]([C:3]1[CH:4]=[C:5]([O:8][Si:22]([CH3:24])([CH3:23])[C:25]([CH3:28])([CH3:27])[CH3:26])[CH:6]=[CH:7][C:2]=1[NH2:1])([O-:11])=[O:10]

Participants

6

Reactant 4

HCID 795ImidazoleHCID 6228DimethylformamideHCID 28928tert-Butyldimethylsilyl chlorideHCID 37588824-Amino-3-Nitrophenol

Product 1

HCID 120422994-(Tert-butyldimethylsilyl)oxy-2-nitroanilineYield 97.3%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

To a mixture of 4-amino-3-nitrophenol (10.07 g, 65.3 mmol) and DMF (20 mL) was added imidazole (11.15 g, 163.8 mmol) followed by t-butyldimethylsilyl chloride (11.82 g, 78.4 mmol) in several portions. After 5 h, the reaction was diluted with EtOAc (150 mL) and washed with water (5×20 mL). The organic layer was MgSO4, dried, filtered, and concentrated. The residue was chromatographed (10% EtOAc/hexanes to 20% EtOAc/hexanes) to give the title compound as a solid (17.06 g, 97%); mp 80-83° C.; IR (CHCl3): 3399, 2932, 1519, 1242, 866 cm−1; NMR (300 MHz, CDCl3): δ0.19 (s, 6H), 0.97 (s, 9H), 6.70 (d, 1H, J=9.0), 6.95 (d, 1H, J=3.0), 7.56 (d, 1H, J=2.7); MS(FD): 268.2.

Workup

  1. washwashed with water (5×20 mL)
  2. customdried
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customThe residue was chromatographed (10% EtOAc/hexanes to 20% EtOAc/hexanes)

Sources & evidence

ORD record
ord-d365a4b8e97447dfba7350ab2a00f6ab
Source dataset
uspto-grants-2004_01
Patent number
US06677369B2

Reaction notes

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