Acetic Acid → Ethyl (4-bromo-2-nitrophenyl)acetate

HRID 422033

Reaction equation

HRID 422033 reaction equation
[CH3:1][O:2][C:3](=[O:19])[CH:4]([C:9]1[CH:14]=[CH:13][C:12]([Br:15])=[CH:11][C:10]=1[N+:16]([O-:18])=[O:17])C(OC)=O.Cl.[C:21](O)(=O)C>>[CH2:1]([O:2][C:3](=[O:19])[CH2:4][C:9]1[CH:14]=[CH:13][C:12]([Br:15])=[CH:11][C:10]=1[N+:16]([O-:18])=[O:17])[CH3:21]

Participants

4

Reactant 3

HCID 176Acetic AcidHCID 313Hydrochloric AcidHCID 157405961,3-Dimethyl 2-(4-bromo-2-nitrophenyl)propanedioate

Product 1

HCID 23247724Ethyl (4-bromo-2-nitrophenyl)acetate

Conditions

Temperature
110 °C

Procedure

To a suspension of 2-(4-bromo-2-nitro-phenyl)-malonic acid dimethyl ester (crude, 8.1 mmol) in acetic acid (10 mL) is added 6N HCl (10 mL). The mixture is heated at 110° C. overnight (about 15 hr). The reaction mixture is evaporated to dryness. The crude is used in the next step without further purification. To a solution of the crude in ethanol (40 mL) is added concentrated H2SO4 (3 drops) and the resulting reaction mixture is heated at reflux over night. Solvent is removed under reduced pressure. It is purified by flash column chromatography. 1H NMR (400 MHz, CDCl3) δ 8.25 (s, 1 H), 7.72-7.7 (m, 1 H), 7.26-7.22 (m, 1 H), 4.23-4.13 (q, 2 H), 3.97 (s, 2 H), 1.29-1.23 (t, 3 H).

Workup

  1. customThe reaction mixture is evaporated to dryness
  2. customThe crude is used in the next step without further purification
  3. additionTo a solution of the crude in ethanol (40 mL) is added concentrated H2SO4 (3 drops)
  4. customthe resulting reaction mixture
  5. temperatureis heated
  6. temperatureat reflux over night
  7. customSolvent is removed under reduced pressure
  8. customIt is purified by flash column chromatography

Sources & evidence

ORD record
ord-aa490170718c48e58721ae2e7a7b0cfe
Source dataset
uspto-grants-2012_01
Patent number
US08101608B2

Linked notes

Loading…