p-Toluenesulfonic acid → Methyl 3-[(2-bromo-5-nitrophenyl)amino]-2-methylprop-2-enoate

HRID 511543Notes

Reaction equation

HRID 511543 reaction equation
[CH3:1][O:2][CH:3]([O:10]C)[CH:4]([CH3:9])[C:5](OC)=O.[Br:12][C:13]1[CH:18]=[CH:17][C:16]([N+:19]([O-:21])=[O:20])=[CH:15][C:14]=1[NH2:22].CC1C=CC(S(O)(=O)=O)=CC=1>C1C=CC=CC=1>[Br:12][C:13]1[CH:18]=[CH:17][C:16]([N+:19]([O-:21])=[O:20])=[CH:15][C:14]=1[NH:22][CH:5]=[C:4]([CH3:9])[C:3]([O:2][CH3:1])=[O:10]

Participants

5

Reactant 3

HCID 6101p-Toluenesulfonic acidHCID 826072-Bromo-5-nitroanilineHCID 3018662Methyl 3,3-dimethoxy-2-methylpropanoate

Product 1

HCID 67254564Methyl 3-[(2-bromo-5-nitrophenyl)amino]-2-methylprop-2-enoateYield 67.5%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

A mixture of methyl 3,3-dimethoxy-2-methylpropionate (10 g, 46 mmol. Commercially available or can be prepared according to Org. Biomol. Chem. 2006, 4, 2945), 2-bromo-5-nitrophenylamine (12 g, 74 mmol) and p-TsOH (50 mg, 0.29 mmol) in benzene (200 mL) was stirred at reflux for 24 h. The reaction mixture was allowed to cool to room temperature. The reaction mixture was concentrated under reduced pressure. The residue was recrystallized from DCM to afford the desired product (9.8 g, yield: 67.5%) as a solid. 1H NMR (DMSO-d6, 400 MHz): δ=1.86 (s, 3 H), 3.29 (s, 3 H), 7.64 (dd, J=2.4, 8.4 Hz, 1H), 7.87 (s, 1 H), 7.88 (d, J=8.4 Hz, 1 H), 8.24 (d, J=2.4 Hz, 1 H).

Workup

  1. customCommercially available or can be prepared
  2. temperatureat reflux for 24 h
  3. concentrationThe reaction mixture was concentrated under reduced pressure
  4. customThe residue was recrystallized from DCM

Sources & evidence

ORD record
ord-e49636706c7d43f8a80ea47f23c14141
Source dataset
uspto-grants-2015_08
Patent number
US09096624B2

Reaction notes

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