Dimethylformamide → tert-butyl N-[2-(3-aminophenoxy)ethyl]carbamate

HRID 1189922Notes

Reaction equation

HRID 1189922 reaction equation
N[C:2]1([OH:8])[CH:7]=[CH:6][CH:5]=[CH:4][CH2:3]1.CC1C=CC(S(O[CH2:20][CH2:21][NH:22][C:23]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:24])(=O)=O)=CC=1.C(=O)([O-])[O-].[Cs+].[Cs+].C[N:37](C=O)C>>[NH2:37][C:4]1[CH:3]=[C:2]([CH:7]=[CH:6][CH:5]=1)[O:8][CH2:20][CH2:21][NH:22][C:23](=[O:24])[O:25][C:26]([CH3:29])([CH3:28])[CH3:27]

Participants

5

Reactant 4

HCID 6228DimethylformamideHCID 10796Cesium carbonateHCID 10781634tert-butyl N-{2-[(4-methylbenzenesulfonyl)oxy]ethyl}carbamateHCID 20474799c1-Aminophenol

Product 1

HCID 11557882tert-butyl N-[2-(3-aminophenoxy)ethyl]carbamate

Procedure

A mixture of 1-aminophenol (1) (207 mg, 1.9 mmol), 2-(tert-butoxycarbonylamino)ethyl 4-methylbenzenesulfonate (2) (500 mg, 1.9 mmol), and cesium carbonate (770 mg, 2.2 mmol) in DMF (6 ml) was stirred at room temperature under argon for 15 hours. The mixture was concentrated under reduced pressure. The residue was partitioned between EtOAc and water. The organic layer was washed with brine, dried over Na2SO4 and concentrated under reduced pressure. Purification by flash chromatography (40 to 60% EtOAc-hexanes gradient) gave tert-butyl 2-(3-aminophenoxy)ethylcarbamate (3) as colorless oil. Yield (220 mg, 58%). 1H NMR (400 MHz, DMSO-d6) δ 6.92 (t, J=5.2 Hz, 1H), 6.85 (t, J=8.0 Hz, 1H), 6.08-6.12 (m, 2H), 6.02-6.04 (m, 1H), 4.99 (bs, 2H), 3.79 (t, J=6.0 Hz, 2H), 3.21 (q, J=6.0 Hz, 2H), 1.36 (s, 9H).

Workup

  1. concentrationThe mixture was concentrated under reduced pressure
  2. customThe residue was partitioned between EtOAc and water
  3. washThe organic layer was washed with brine
  4. dry with materialdried over Na2SO4
  5. concentrationconcentrated under reduced pressure
  6. customPurification by flash chromatography (40 to 60% EtOAc-hexanes gradient)

Sources & evidence

ORD record
ord-e889ecca73cc4441ad9d373a74515f6b
Source dataset
uspto-grants-2014_03
Patent number
US08674137B2

Reaction notes

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