Benzyl Bromide → 2-(benzyloxy)-4-nitroaniline

HRID 1814293Notes

Reaction equation

HRID 1814293 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][C:3]=1[OH:11].CC(C)([O-])C.[K+].[CH2:18](Br)[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1>C1COCC1>[CH2:18]([O:11][C:3]1[CH:4]=[C:5]([N+:8]([O-:10])=[O:9])[CH:6]=[CH:7][C:2]=1[NH2:1])[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1

Participants

5

Reactant 3

HCID 7498Benzyl BromideHCID 49847212-Amino-5-NitrophenolHCID 23665647Potassium tert-butoxide

Product 1

HCID 27757972-(benzyloxy)-4-nitroaniline

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

The starting 2-amino-5-nitrophenol (21.2 g, 0.14 mol) was dissolved in 350 mL THF. Solid potassium t-butoxide (15.85 g, 0.141 mol) was added slowly, with vigorous stirring. Then a solution of benzylbromide (in 150 mL THF) was added slowly and stirred at room temperature for 2 days. The solvent was removed and the crude oil poured into water (ca. 500 mL) and 3:1 ethyl acetate/methylene chloride (ca. 200 mL). The solid precipitate was filtered off and dried, then recrystallized in toluene to give 2-benzyloxy-4-nitro-phenylamine (9.1 g). The aqueous and organic layers were separated and the aqueous layer was extracted twice with 3:1 ethyl acetate/methylene chloride. The combined organic layers were washed with 5% sodium hydroxide (which formed three layers, and the middle layer contained the desired material by TLC), then the desired layer was washed twice with water, then brine, and dried over anhydrous magnesium sulfate, filtered and the solvent removed. The solid was recrystallized in toluene, filtered and dried to yield 12 g of 2-benzyloxy-4-nitro-phenylamine. (The total yield was 62%.). 1H NMR (CDCl3) 7.9-7.7 (m, 2H), 7.5-7.3 (m, 5H), 6.65 (d, 1H, J=8.68 Hz), 5.15 (s, 2H), 4.57 (br, 2H).

Workup

  1. customThe solvent was removed
  2. additionthe crude oil poured into water (ca. 500 mL) and 3:1 ethyl acetate/methylene chloride (ca. 200 mL)
  3. filtrationThe solid precipitate was filtered off
  4. customdried
  5. customrecrystallized in toluene

Sources & evidence

ORD record
ord-ea240b153aed44f08b932efa78150adc
Source dataset
uspto-grants-2005_04
Patent number
US06875765B2

Reaction notes

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