Triethylamine → benzyl (2E)-2-(acetylamino)-3-(4-amino-3-ethylphenyl)-2-propenoate

HRID 488636Notes

Reaction equation

HRID 488636 reaction equation
[C:1]([NH:4][C:5](=[CH2:16])[C:6]([O:8][CH2:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)=[O:7])(=[O:3])[CH3:2].CCN(CC)CC.Br[C:25]1[CH:31]=[CH:30][C:28]([NH2:29])=[C:27]([CH2:32][CH3:33])[CH:26]=1>C(#N)C.CC([O-])=O.CC([O-])=O.[Pd+2]>[C:1]([NH:4]/[C:5](=[CH:16]/[C:25]1[CH:31]=[CH:30][C:28]([NH2:29])=[C:27]([CH2:32][CH3:33])[CH:26]=1)/[C:6]([O:8][CH2:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)=[O:7])(=[O:3])[CH3:2]

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 28012834-Bromo-2-ethylanilineHCID 14382052Benzyl 2-(acetylamino)acrylate

Product 1

HCID 11013183benzyl (2E)-2-(acetylamino)-3-(4-amino-3-ethylphenyl)-2-propenoateYield 25.7%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 6342AcetonitrileSolvent

Procedure

To benzyl 2-(acetylamino)acrylate (80.0 mmol) in acetonitrile (200 mL) was added Pd(OAc)2 (488 mg, 2.18 mmol), (o-Tol)3P (1.32 g, 4.35 mmol), Et3N (20 mL) followed by addition of 4-bromo-2-ethylaniline (14.5 g, 72.5 mmol). The reaction mixture was heated to reflux overnight, concentrated under reduce pressure, taken up in ethyl acetate, washed with aqueous NaHCO3, dried (MgSO4), filtered and concentrated under reduced pressure. The residue was precipitated from ethyl acetate/hexane to provide the titled compound (6.3 g). The filtrate was precipitated a second time to provide and additional 5 g of the titled compound. MS (ESI(+)) m/e 339 (M+H)+; 1H NMR (300 MHz, DMSO-d6) δ 9.31 (s, 1H), 7.40-7.20 (m, 8H), 6.59 (d, 1H), 5.52 (s, 2H), 5.16 (s, 2H), 2.42 (q, 2H), 1.98 (s, 3H), 1.13 (t, 3H).

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureto reflux overnight
  3. concentrationconcentrated
  4. washwashed with aqueous NaHCO3
  5. dry with materialdried (MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customThe residue was precipitated from ethyl acetate/hexane

Sources & evidence

ORD record
ord-2c6233ae1ae8454a8dc4faa31306c024
Source dataset
uspto-grants-2005_12
Patent number
US06972340B2

Reaction notes

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