Tert-butyl 4-chloro-3-nitrobenzoate → Tert-butyl 4-(ethylamino)-3-nitrobenzoate

HRID 1241966Notes

Reaction equation

HRID 1241966 reaction equation
[C:1]([O:5][C:6](=[O:17])[C:7]1[CH:12]=[CH:11][C:10](Cl)=[C:9]([N+:14]([O-:16])=[O:15])[CH:8]=1)([CH3:4])([CH3:3])[CH3:2].[CH2:18]([NH2:20])[CH3:19].C1COCC1>C1COCC1>[C:1]([O:5][C:6](=[O:17])[C:7]1[CH:12]=[CH:11][C:10]([NH:20][CH2:18][CH3:19])=[C:9]([N+:14]([O-:16])=[O:15])[CH:8]=1)([CH3:4])([CH3:3])[CH3:2]

Participants

4

Reactant 2

HCID 10611184Tert-butyl 4-chloro-3-nitrobenzoateHCID 66726184Ethylamine tetrahydrofuran

Product 1

HCID 20626666Tert-butyl 4-(ethylamino)-3-nitrobenzoateYield 100.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
65 °C

Procedure

4-Chloro-3-nitrobenzoic acid tert-butyl ester (3.0 g, 11.6 mmol), prepared according to a published procedure [WO 9707101], was cautiously added to a solution of 2.0 M EtNH2/THF (20 mL, 40 mmol) and TEA (2.0 mL, 14 mmol) in anhydrous THF (30 mL). The resulting mixture was heated at 65° C. for 3 h, cooled, concentrated under reduced pressure, diluted with DCM (200 mL), washed with water (2×100 mL) and brine (50 mL), dried over anhydrous Na2SO4 and concentrated to give the title compound (3.1 g, 99%) as a yellow solid, which was used without further purification. 1H-NMR (CDCl3): δ 8.80 (1H, d), 8.24 (1H, br s), 8.02 (1H, dd), 6.84 (1H, d), 3.41 (2H, m), 1.59 (9H, s), 1.40 (3H, t).

Workup

  1. temperaturecooled
  2. concentrationconcentrated under reduced pressure
  3. additiondiluted with DCM (200 mL)
  4. washwashed with water (2×100 mL) and brine (50 mL)
  5. dry with materialdried over anhydrous Na2SO4
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-4d9f744c303c4972beaa8673c09d0d6d
Source dataset
uspto-grants-2006_10
Patent number
US07115640B2

Reaction notes

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