4-Nitrophenol → tert-Butyl [2-(4-nitrophenoxy)ethyl]carbamate

HRID 379693Notes

Reaction equation

HRID 379693 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][C:7]([OH:10])=[CH:6][CH:5]=1)([O-:3])=[O:2].[C:11]([O:15][C:16]([NH:18][CH2:19][CH2:20]O)=[O:17])([CH3:14])([CH3:13])[CH3:12].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CCOC(N=NC(OCC)=O)=O>O1CCCC1>[C:11]([O:15][C:16]([NH:18][CH2:19][CH2:20][O:10][C:7]1[CH:8]=[CH:9][C:4]([N+:1]([O-:3])=[O:2])=[CH:5][CH:6]=1)=[O:17])([CH3:14])([CH3:13])[CH3:12]

Participants

6

Reactant 4

HCID 9804-NitrophenolHCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 2733206tert-butyl N-(2-hydroxyethyl)carbamate

Product 1

HCID 18173671tert-Butyl [2-(4-nitrophenoxy)ethyl]carbamateYield 72.6%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

4-Nitrophenol (4.01 g), 2-(tert-butoxycarbonylamino)ethanol (4.65 g) and triphenylphosphine (7.55 g) were dissolved into tetrahydrofuran (50 ml) and the solution was ice cooled. Azo dicarboxylic acid diethyl (5.52 g) dissolved in tetrahydrofuran (5 ml) was added drop-wise into the ice-cooled solution. After being stirred for one hour at room temperature, the reaction mixture was concentrated under vacuum. Residue was dissolved into ethyl acetate (50 ml). Hexane (400 ml) was added to the ethyl acetate solution and insoluble matter formed was removed from solution by filtration. Filtrate was concentrated under vacuum to small volume. Concentrate was purified by silica-gel column chromatography using ethyl acetate:hexane (1:1) as the solvent system to obtain N-(tert-butoxycarbonyl)-2-(4-nitrophenoxy)ethylamine (5.91 g) as color-less oily substance.

Workup

  1. temperaturecooled
  2. temperaturecooled solution
  3. concentrationthe reaction mixture was concentrated under vacuum
  4. dissolutionResidue was dissolved into ethyl acetate (50 ml)
  5. additionHexane (400 ml) was added to the ethyl acetate solution and insoluble matter
  6. customformed
  7. customwas removed from solution by filtration
  8. concentrationFiltrate was concentrated under vacuum to small volume
  9. concentrationConcentrate
  10. customwas purified by silica-gel column chromatography

Sources & evidence

ORD record
ord-88b1ca34415847179a460dafe3905eb7
Source dataset
uspto-grants-2001_10
Patent number
US06300368B1

Reaction notes

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