Ethyl Acetoacetate → 3-(3-Benzyloxy-4-bromo-phenylamino)-but-2-enoic acid ethyl ester

HRID 1006173Notes

Reaction equation

HRID 1006173 reaction equation
[CH2:1]([O:8][C:9]1[CH:10]=[C:11]([NH2:16])[CH:12]=[CH:13][C:14]=1[Br:15])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:17]([O:23][CH2:24][CH3:25])(=[O:22])[CH2:18][C:19]([CH3:21])=O>C1CCCCC1.O.C1(C)C=CC(S(O)(=O)=O)=CC=1>[CH2:24]([O:23][C:17](=[O:22])[CH:18]=[C:19]([NH:16][C:11]1[CH:12]=[CH:13][C:14]([Br:15])=[C:9]([O:8][CH2:1][C:2]2[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=2)[CH:10]=1)[CH3:21])[CH3:25]

Participants

5

Reactant 2

HCID 8868Ethyl AcetoacetateHCID 146595013-(Benzyloxy)-4-bromoaniline

Product 1

HCID 694724593-(3-Benzyloxy-4-bromo-phenylamino)-but-2-enoic acid ethyl esterYield 106.2%

Reagents, catalysts & solvents 2

HCID 521998p-Toluenesulfonic acid monohydrateCatalystHCID 8078CyclohexaneSolvent

Procedure

To a mixture of 3-benzyloxy-4-bromo-phenylamine (55.7 g, 0.168 mol) and ethyl acetoacetate (23.4 mL, 0.185 mol) in cyclohexane was added toluene-4-sulfonic acid monohydrate (0.320 g, 1.68 mmol) The reaction mixture was refluxed during 6 h and the water was azeotropically removed. The reaction mixture was then partitioned between ethyl acetate and an aqueous solution of sodium hydrogenocarbonate. The organic layer was washed with brine, dried over sodium sulfate, filtered and the solvents were evaporated under vacuum. 69.6 g of the title compound were obtained. Black oil, ISP-MS: m/e=392.2 ([M+H]+).

Workup

  1. temperaturewas refluxed during 6 h
  2. customthe water was azeotropically removed
  3. customThe reaction mixture was then partitioned between ethyl acetate
  4. washThe organic layer was washed with brine
  5. dry with materialdried over sodium sulfate
  6. filtrationfiltered
  7. customthe solvents were evaporated under vacuum

Sources & evidence

ORD record
ord-9ca7bb1d7e8141f1a861800868f627b7
Source dataset
uspto-grants-2004_09
Patent number
US06787558B2

Reaction notes

Loading…