Hydrochloric Acid → HCID 86702686, compound

HRID 1897863Notes

Reaction equation

HRID 1897863 reaction equation
[OH:1][C:2]1[CH:3]=[C:4]([CH3:15])[C:5]([N+:12]([O-])=O)=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8].[H][H].[ClH:18].O1CCOCC1>[Pd].C1COCC1.CCOC(C)=O.CO>[ClH:18].[NH2:12][C:5]1[C:4]([CH3:15])=[CH:3][C:2]([OH:1])=[CH:11][C:6]=1[C:7]([O:9][CH3:10])=[O:8].[ClH:18].[NH2:12][C:5]1[C:4]([CH3:15])=[CH:3][C:2]([OH:1])=[CH:11][C:6]=1[C:7]([OH:9])=[O:8]

Participants

10

Reactant 4

HCID 313Hydrochloric AcidHCID 312751,4-DioxaneHCID 86702687HCID 86702687, compoundHCID 178418361HCID 178418361, compound3×

Product 2

HCID 86702685HCID 86702685, compoundHCID 86702686HCID 86702686, compoundYield 90%

Reagents, catalysts & solvents 4

HCID 23938PalladiumCatalystHCID 887MethanolSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
20 °C

Procedure

Palladium on carbon (5 wt. %, wet, contains ˜50% water, 2.4 g, 0.56 mmol, 0.005 eq) is charged into a 300 mL Parr bomb. Then, methyl 5-hydroxy-3-methyl-2-nitrobenzoate (23.2 g, 0.11 mol, 1 eq) and MeOH (80 mL) are charged. The bomb is sealed, and pressurized/vented three times with hydrogen, and pressured with 100 psi hydrogen. The reaction mixture is stirred, until the hydrogen pressure is not dropping. The bomb is opened, and an HPLC sample shows that the reaction is complete. The mixture is diluted with 80 ml of THF and filtered through a Celite pad. The solution is concentrated under vacuum and solvent is switched to EtOAc. To the suspension in EtOAc (150 mL) at 15° C., HCl in dioxane (4M, 36 mL, 0.14 mol, 1.3 eq) is charged at a rate that the internal temperature is below 30° C. The suspension is stirred at 20° C. for 2 hour. The slurry is filtered. The solid is dried under vacuum to provide the desired product, 2-amino-5-hydroxy-3-methylbenzoate hydrochloride (21.5 g, 90% yield).

Workup

  1. customThe bomb is sealed
  2. filtrationfiltered through a Celite pad
  3. concentrationThe solution is concentrated under vacuum and solvent
  4. customis below 30° C
  5. filtrationThe slurry is filtered
  6. customThe solid is dried under vacuum

Sources & evidence

ORD record
ord-54b36d7a57b3453f8436bbfcacdc0079
Source dataset
uspto-grants-2013_08
Patent number
US08519176B1

Reaction notes

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