Hydrochloric Acid → 4,6-Diaminoresorcinol Dihydrochloride

HRID 1492088Notes

Reaction equation

HRID 1492088 reaction equation
[Cl:1][C:2]1[C:8]([OH:9])=[C:7]([N+:10]([O-])=O)[CH:6]=[C:5]([N+:13]([O-])=O)[C:3]=1[OH:4].CC([O-])=O.[Na+].[H][H].Cl.O.O.[Cl:26][Sn]Cl>O.[Pd].C(O)(=O)C>[ClH:1].[ClH:26].[NH2:10][C:7]1[C:8]([OH:9])=[CH:2][C:3]([OH:4])=[C:5]([NH2:13])[CH:6]=1

Participants

9

Reactant 5

HCID 313Hydrochloric AcidHCID 61436Stannous chloride dihydrateHCID 517045Sodium AcetateHCID 111072901,3-Benzenediol, 2-chloro-4,6-dinitro-HCID 178418361HCID 178418361, compound

Product 1

HCID 27336484,6-Diaminoresorcinol Dihydrochloride

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 176Acetic AcidSolventHCID 962WaterSolvent2×

Procedure

A one-liter Hastalloy C autoclave equipped with a gas dispersion stirrer and cooling coil is charged with 117.3 g (0.5 mole) of 2-chloro-4,6-dinitroresorcinol, 400 ml of glacial acetic acid, 41 g (0.5 mole) of NaOAc, 7.0 g of 10 percent palladium over carbon and 100 mL of H2O. The sealed reactor is charged with 400 psi of H2 and the temperature is brought to 40° C. and maintained between 40° C. and 50° C. during the course of the reaction. After a brief induction period, the uptake of hydrogen becomes extremely rapid and H2 pressure is maintained between 100-400 psi during the reaction. Upon completion, no further uptake of H2 is observed. The reactor is cooled to room temperature, opened and 400 mL of concentrated HCl containing 10 g of SnCl2.2H2O is added to the reaction mixture. The crude product with the catalyst is isolated by filtration. This material is dissolved in 200 g of H2O at 85° C. and the catalyst is removed by filtration. H2O (100-300 mL) is added to the filtrate along with 500 mL of HCl and the catalyst-free material is precipitated from the brown solution. Recrystallization is carried out in the existing solvent or the semi-pure material can be isolated and air dried to afford 100 g of crude diaminoresorcinol dihydrochloride, (96.8 mole percent yield based on the 2-chloro-4,6-dinitroresorcinol.

Workup

  1. customA one-liter Hastalloy C autoclave equipped with a gas dispersion stirrer
  2. temperaturecooling coil
  3. additionThe sealed reactor is charged with 400 psi of H2
  4. customis brought to 40° C.
  5. temperaturemaintained between 40° C. and 50° C. during the course of the reaction
  6. temperatureH2 pressure is maintained between 100-400 psi during the reaction
  7. customThe crude product with the catalyst is isolated by filtration
  8. customthe catalyst is removed by filtration
  9. additionH2O (100-300 mL) is added to the filtrate along with 500 mL of HCl
  10. customthe catalyst-free material is precipitated from the brown solution
  11. customRecrystallization
  12. customthe semi-pure material can be isolated
  13. customair dried

Sources & evidence

ORD record
ord-3399c00e20134d98b0d72dea10a4eae1
Source dataset
uspto-grants-1994_12
Patent number
US05371291

Reaction notes

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