p-Anisoyl chloride → N-(2-Amino-5-bromo-phenyl)-4-methoxy-benzamide

HRID 252823Notes

Reaction equation

HRID 252823 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]([N+:9]([O-])=O)=[C:6]([NH2:8])[CH:7]=1.[CH3:12][O:13][C:14]1[CH:22]=[CH:21][C:17]([C:18](Cl)=[O:19])=[CH:16][CH:15]=1.O.O.Cl[Sn]Cl>C1COCC1>[NH2:9][C:5]1[CH:4]=[CH:3][C:2]([Br:1])=[CH:7][C:6]=1[NH:8][C:18](=[O:19])[C:17]1[CH:21]=[CH:22][C:14]([O:13][CH3:12])=[CH:15][CH:16]=1

Participants

5

Reactant 3

HCID 7477p-Anisoyl chlorideHCID 61436Stannous chloride dihydrateHCID 53147665-Bromo-2-nitroaniline

Product 1

HCID 59736778N-(2-Amino-5-bromo-phenyl)-4-methoxy-benzamideYield 85%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
90 °C

Procedure

In aflame dried, round bottom flask, 5-bromo-2-nitro-aniline (2) (10.66 g, 49.09 mmol), (scheme 1, Example 1), and 4-methoxybenzoyl chloride (8.37 g, 49.09 mmol) were added. The mixture was heated to 90° C. The melted solids were stirred overnight to give a yellow-brown solid. THF (250 mL) was then added and the solution was treated with SnCl2.2H2O (55.38 g, 245.45 mmol, 5.0 eq) and stirred at room temperature for 2 hrs. Approx. half of the THF was evaporated then 200 mL of EtOAc and 100 mL sat. NaHCO3 were added. The precipitated tin salt was taken out by filtration and a work-up was done on the filtrate with EtOAc. The combined organic layers were washed with water and brine and dried over MgSO4. Most of the EtOAc was evaporated then hexane was added and the precipitate was collected by filtration to give the title compound 114 as a beige powder (13.40 g, 85% yield). 1H NMR (DMSO-d6) δ(ppm): 9.52 (s, 1H), 7.93 (d, J=9.0 Hz, 2H), 7.34 (d, J=2.3 Hz, 1H), 7.08 (dd. J=8.6, 2.3 Hz, 1H), 7.02 (d, J=9.0 Hz, 2H), 6.71 (d, J=8.6 Hz, 1H) 5.10 (s, 2H), 3.82 (s, 3H).

Workup

  1. customto give a yellow-brown solid
  2. stirringstirred at room temperature for 2 hrs
  3. customApprox. half of the THF was evaporated
  4. addition200 mL of EtOAc and 100 mL sat. NaHCO3 were added
  5. filtrationThe precipitated tin salt was taken out by filtration
  6. washThe combined organic layers were washed with water and brine
  7. dry with materialdried over MgSO4
  8. customMost of the EtOAc was evaporated
  9. additionhexane was added
  10. filtrationthe precipitate was collected by filtration

Sources & evidence

ORD record
ord-3599de0a3f5041768cb7f49e8f53149f
Source dataset
uspto-grants-2011_01
Patent number
US07868205B2

Reaction notes

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