Acetic Acid → 5-amino-2,4-dichlorobenzoic acid

HRID 336424Notes

Reaction equation

HRID 336424 reaction equation
O.[Sn](Cl)Cl.[Cl:5][C:6]1[CH:14]=[C:13]([Cl:15])[C:12]([N+:16]([O-])=O)=[CH:11][C:7]=1[C:8]([OH:10])=[O:9].C([O-])(O)=O.[Na+].CC(O)=O>CCO>[Cl:5][C:6]1[CH:14]=[C:13]([Cl:15])[C:12]([NH2:16])=[CH:11][C:7]=1[C:8]([OH:10])=[O:9]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 516892Sodium BicarbonateHCID 7966502,4-dichloro-5-nitrobenzoic acidHCID 43835034Tin dichloride dihydrate

Product 1

HCID 52002455-amino-2,4-dichlorobenzoic acidYield 96%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
70 °C

Procedure

Tin(II) Chloride hydrate (50 g, 0.29 mol) was added to a solution of 2,4-dichloro-5-nitrobenzoic acid 1-2 (10.0 g, 0.045 mol) in EtOH (200 mL). The mixture was stirred for 70° C. for 30 min, cooled and poured onto ice. The pH of the mixture was adjusted to 8 using saturated aqueous NaHCO3. The suspension was left to stir at room temperature for 5 h and re-acidified to pH 5 with glacial AcOH. The resulting white suspension was continuously washed with EtOAc, the extracts combined, washed with brine, dried over Na2SO4, filtered and concentrated to afford the desired amine 1-3 as an off-white solid (8.8 g, 96%). 1H NMR (400 MHz, CD3OD) δ7.27 (s, 1H), 7.30 (s, 1H).

Workup

  1. temperaturecooled
  2. additionpoured onto ice
  3. waitThe suspension was left
  4. washThe resulting white suspension was continuously washed with EtOAc
  5. washwashed with brine
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-84e22c24c2d64816ab5b20f7c16988f2
Source dataset
uspto-grants-2014_11
Patent number
US08889695B2

Reaction notes

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