Stannous chloride dihydrate → Methyl 2-[(3,4-diaminophenyl)carbonyl]benzoate

HRID 2367112Notes

Reaction equation

HRID 2367112 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]([C:10]2[CH:19]=[CH:18][CH:17]=[CH:16][C:11]=2[C:12]([O:14][CH3:15])=[O:13])=[O:9])=[CH:4][C:3]=1[N+:20]([O-])=O.O.O.[Sn](Cl)Cl>C(O)(=O)C>[NH2:20][C:3]1[CH:4]=[C:5]([C:8]([C:10]2[CH:19]=[CH:18][CH:17]=[CH:16][C:11]=2[C:12]([O:14][CH3:15])=[O:13])=[O:9])[CH:6]=[CH:7][C:2]=1[NH2:1]

Participants

4

Reactant 2

HCID 61436Stannous chloride dihydrateHCID 14994663Methyl 2-[(4-amino-3-nitrophenyl)carbonyl]benzoate

Product 1

HCID 67044285Methyl 2-[(3,4-diaminophenyl)carbonyl]benzoateYield 37%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Conditions

Temperature
75 °C

Procedure

Methyl 2-[(4-amino-3-nitrophenyl)carbonyl]benzoate (0.74 g, 2.47 mmol) was dissolved in acetic acid (9 mL) at 45° C. and tin (II) chloride dihydrate (2.22 g, 9.84 mmol) was added. The mixture was stirred at 75° C. for 7 h and then was concentrated in vacuo. The residue was transferred to an Erlenmeyer flask using a little ethyl acetate and diluted with ether (20 mL). The mixture was stirred while cooling in an ice-water bath and sodium hydroxide (50% solution in water) (6 mL) was added dropwise. The solid which formed was removed by filtration and was washed with hot ethyl acetate. The combined filtrate was concentrated in vacuo and the residue was partitioned between ethyl acetate and water. The organic portion was washed with brine, dried over sodium sulfate, filtered and concentrated in vacuo to afford methyl 2-[(3,4-diaminophenyl)carbonyl]benzoate as a yellow solid (0.245 g, 0.907 mmol, 37% yield). 1H NMR (400 MHz, d6-DMSO): 7.87 (dd, 1H), 7.65 (td, 1H), 7.57 (td, 1H), 7.32 (dd, 1H), 6.93 (d, 1H), 6.66 (dd, 1H), 6.44 (d, 1H), 5.49 (s, 2H), 4.69 (s, 2H), 3.57 (s, 3H); MS (EI) for C15H14N2O3: 293 (MNa+).

Workup

  1. concentrationwas concentrated in vacuo
  2. additiondiluted with ether (20 mL)
  3. stirringThe mixture was stirred
  4. temperaturewhile cooling in an ice-water bath
  5. additionsodium hydroxide (50% solution in water) (6 mL) was added dropwise
  6. customThe solid which formed
  7. customwas removed by filtration
  8. washwas washed with hot ethyl acetate
  9. concentrationThe combined filtrate was concentrated in vacuo
  10. customthe residue was partitioned between ethyl acetate and water
  11. washThe organic portion was washed with brine
  12. dry with materialdried over sodium sulfate
  13. filtrationfiltered
  14. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-de046fac3611406ab0088a192c9bcc1a
Source dataset
uspto-grants-2014_04
Patent number
US08697737B2

Reaction notes

Loading…