Water → (Z)-ethyl 3-(2-amino-5-bromophenyl)but-2-enoate

HRID 1504412Notes

Reaction equation

HRID 1504412 reaction equation
[C:1]([O:6][CH2:7][CH3:8])(=[O:5])/[CH:2]=[CH:3]/[CH3:4].[Br:9][C:10]1[CH:16]=[CH:15][C:13]([NH2:14])=[C:12](I)[CH:11]=1.CCN(C(C)C)C(C)C.O>CN(C=O)C>[NH2:14][C:13]1[CH:15]=[CH:16][C:10]([Br:9])=[CH:11][C:12]=1/[C:3](/[CH3:4])=[CH:2]\[C:1]([O:6][CH2:7][CH3:8])=[O:5]

Participants

6

Reactant 4

HCID 962WaterHCID 81531DiisopropylethylamineHCID 429065Ethyl trans-crotonateHCID 8239344-Bromo-2-iodoaniline

Product 1

HCID 117746854(Z)-ethyl 3-(2-amino-5-bromophenyl)but-2-enoateYield 40%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A solution of Pd(Amphos)2Cl2 (1.188 g, 1.678 mmol), ethyl crotonate (5.01 ml, 40.3 mmol), 4-bromo-2-iodoaniline (Spectrum Bioscience, 10.000 g, 33.6 mmol), and n,n-diisopropylethylamine (7.03 ml, 40.3 mmol) in 6 mL DMF was heated to 90° C. for 6 hours. The reaction mixture was then poured into water and was extracted with DCM. The organics were dried over MgSO4 and concentrated. Purification of the crude residue by silica gel column chromatography (0-100% EtOAc/heptane) gave (Z)-ethyl 3-(2-amino-5-bromophenyl)but-2-enoate (3.817 g, 13.43 mmol, 40.0% yield) with minor impurities. m/z (ESI) 286.1 (M+H)+.

Workup

  1. extractionwas extracted with DCM
  2. dry with materialThe organics were dried over MgSO4
  3. concentrationconcentrated
  4. customPurification of the crude residue by silica gel column chromatography (0-100% EtOAc/heptane)

Sources & evidence

ORD record
ord-2125b2aa21ee4c93a328673ebf0e2fb1
Source dataset
uspto-grants-2015_12
Patent number
US09212182B2

Reaction notes

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