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

HRID 1829773Notes

Reaction equation

HRID 1829773 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-efc92bd078084cfa99170fc0548d195c
Source dataset
uspto-grants-2006_06
Patent number
US07064134B2

Reaction notes

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