Benzyl Alcohol → 4-Benzyloxy-2-nitroaniline

HRID 492246Notes

Reaction equation

HRID 492246 reaction equation
N(C(OCC)=O)=NC(OCC)=O.[NH2:13][C:14]1[CH:19]=[CH:18][C:17]([OH:20])=[CH:16][C:15]=1[N+:21]([O-:23])=[O:22].[CH2:24](O)[C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C(OCC)(=O)C.C1COCC1>[CH2:24]([O:20][C:17]1[CH:18]=[CH:19][C:14]([NH2:13])=[C:15]([N+:21]([O-:23])=[O:22])[CH:16]=1)[C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1

Participants

7

Reactant 4

HCID 244Benzyl AlcoholHCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 37588824-Amino-3-Nitrophenol

Product 1

HCID 2614974-Benzyloxy-2-nitroanilineYield 75.7%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

At 0° C., diethyl azodicarboxylate (3.4 mL) was added to a THF solution (13 mL) of 4-amino-3-nitrophenol (1.0 g), benzyl alcohol (1.0 g) and triphenyl phosphine (1.9 g), and stirred at room temperature for 5 hours. The reaction liquid was diluted with ethyl acetate, and the organic layer was washed with aqueous 1 N sodium hydroxide solution, aqueous saturated sodium hydrogencarbonate solution and saturated saline water in that order. The organic layer was dried with anhydrous sodium sulfate, and then concentrated under reduced pressure. The resulting residue was purified through silica gel column chromatography (hexane/ethyl acetate=2/8 to 3/7) to obtain 4-(benzyloxy)-2-nitroaniline (1.2 g) as a red solid.

Workup

  1. customThe reaction liquid
  2. washthe organic layer was washed with aqueous 1 N sodium hydroxide solution, aqueous saturated sodium hydrogencarbonate solution and saturated saline water in that order
  3. dry with materialThe organic layer was dried with anhydrous sodium sulfate
  4. concentrationconcentrated under reduced pressure
  5. customThe resulting residue was purified through silica gel column chromatography (hexane/ethyl acetate=2/8 to 3/7)

Sources & evidence

ORD record
ord-81b27865c06b4b428c8b38c91f5426ab
Source dataset
uspto-grants-2009_05
Patent number
US07531668B2

Reaction notes

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