Benzenesulfonic acid, 4-methyl-, compd. with pyridine (1:1) → ethyl (2Z)-3-[(4-bromo-3-methoxyphenyl)amino]-3-phenylacrylate

HRID 1360103Notes

Reaction equation

HRID 1360103 reaction equation
[CH3:1][NH:2]/[C:3](/[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)=[CH:4]\[C:5]([O:7][CH2:8][CH3:9])=[O:6].[Br:16][C:17]1[CH:23]=[CH:22]C(N)=[CH:19][C:18]=1[O:24][CH3:25].CC1C=CC(S([O-])(=O)=O)=CC=1.C1C=C[NH+]=CC=1>C(Cl)Cl>[Br:16][C:17]1[CH:23]=[CH:22][C:1]([NH:2]/[C:3](/[C:10]2[CH:11]=[CH:12][CH:13]=[CH:14][CH:15]=2)=[CH:4]\[C:5]([O:7][CH2:8][CH3:9])=[O:6])=[CH:19][C:18]=1[O:24][CH3:25]

Participants

5

Reactant 3

HCID 466102Benzenesulfonic acid, 4-methyl-, compd. with pyridine (1:1)HCID 70182544-Bromo-3-methoxyanilineHCID 10976613ethyl (2Z)-3-(methylamino)-3-phenylacrylate

Product 1

HCID 57617098ethyl (2Z)-3-[(4-bromo-3-methoxyphenyl)amino]-3-phenylacrylateYield 87.3%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of ethyl (2Z)-3-(methylamino)-3-phenylacrylate (4.47 g, 21.77 mmol) in DCM (100 mL) was added 4-bromo-3-methoxyaniline (4 g, 19.80 mmol) and PPTS (5.47 g, 21.77 mmol). The mixture was then heated to reflux for 24 h. At this time crude 1H NMR revealed nearly complete consumption of the aniline. The reaction was then cooled to RT, filtered, and the solvent was removed in vacuo. The crude product was purified on silica (75% DCM/hexanes) to yield ethyl (2Z)-3-[(4-bromo-3-methoxyphenyl)amino]-3-phenylacrylate (6.5 g, 87%) which was used as is in subsequent reactions. 1H NMR (500 MHz, CDCl3) ppm: 10.32 (br s, 1H), 7.32 (m, 5H), 7.20 (d, J=8.5 Hz, 1H), 6.19 (dd, J=8.5 Hz, 2.5 Hz, 1H), 6.11 (d, J=2.5 z, 1H), 5.03 (s, 1H), 4.21 (q, J=7.0 Hz, 2H), 3.50 (s, 3H), 1.32 (t, J=7.0 Hz, 3H).

Workup

  1. temperatureThe mixture was then heated
  2. temperatureto reflux for 24 h
  3. customconsumption of the aniline
  4. filtrationfiltered
  5. customthe solvent was removed in vacuo
  6. customThe crude product was purified on silica (75% DCM/hexanes)

Sources & evidence

ORD record
ord-c446a2855e364668ba8487f6ba1bf70e
Source dataset
uspto-grants-2011_02
Patent number
US07879797B2

Reaction notes

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