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

HRID 1374777Notes

Reaction equation

HRID 1374777 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-5689835f00dc4779903741eb58ac23f9
Source dataset
uspto-grants-2007_01
Patent number
US07166589B2

Reaction notes

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