Hydrochloric Acid → HCID 66929481, compound

HRID 1909449Notes

Reaction equation

HRID 1909449 reaction equation
[H][H].[CH3:3][O:4][C:5]1[CH:10]=[CH:9][C:8]([C:11]2[CH:12]=[N:13][O:14][C:15]=2[C:16]2[CH:21]=[C:20]([O:22][CH3:23])[C:19]([O:24][CH3:25])=[C:18]([O:26][CH3:27])[CH:17]=2)=[CH:7][C:6]=1[N+:28]([O-])=O.C1COCC1.[ClH:36]>CO.[Pd]>[ClH:36].[CH3:3][O:4][C:5]1[CH:10]=[CH:9][C:8]([C:11]2[CH:12]=[N:13][O:14][C:15]=2[C:16]2[CH:17]=[C:18]([O:26][CH3:27])[C:19]([O:24][CH3:25])=[C:20]([O:22][CH3:23])[CH:21]=2)=[CH:7][C:6]=1[NH2:28]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 8028TetrahydrofuranHCID 44439005HCID 44439005, compoundHCID 178418361HCID 178418361, compound

Product 1

HCID 66929481HCID 66929481, compound

Reagents, catalysts & solvents 2

HCID 887MethanolSolvent2×HCID 23938PalladiumSolvent

Procedure

A 200-mL round-bottom flask equipped with T-bore stopcock connected to a balloon with hydrogen was charged with 4 (4.44 g, 11.5 mmol) and THF (40 mL), and a mixture was stirred to dissolve a substrate. Methanol (22 mL), solution of HCl in methanol (1M, 22 mL) and palladium, 10 wt % on activated carbon (532 mg, 12 wt %) were added to the flask, the system was evacuated and stirred under atmosphere of hydrogen for 2 hours. TLC indicated completion of reaction (Hexane/EtOAc, 2:1, developed two times). Catalyst was filtered out and washed with methanol (15 mL×3). Filtrate was diluted with 2-propanol (20 mL) and concentrated under reduced pressure to ˜20 mL volume. A resulted suspension was diluted with EtOAc (20 mL), a solid was filtered out, washed with EtOAc (20×2) and dried to give crude amine hydrochloride 5 as a yellow solid, 3.3 g (80%), LC purity 97.1%. The solid was refluxed in ethanol (50 mL) for 15 min to dissolve colored impurities. A cooled suspension was filtered out, washed with EtOAc (20×2) and vacuum-dried to obtain a creamy-colored solid, 2.9 g (70%), LC purity 99.1%.

Workup

  1. customA 200-mL round-bottom flask equipped with T-bore stopcock
  2. dissolutionto dissolve a substrate
  3. customthe system was evacuated
  4. stirringstirred under atmosphere of hydrogen for 2 hours
  5. customcompletion of reaction (Hexane/EtOAc, 2:1, developed two times)
  6. filtrationCatalyst was filtered out
  7. washwashed with methanol (15 mL×3)
  8. additionFiltrate was diluted with 2-propanol (20 mL)
  9. concentrationconcentrated under reduced pressure to ˜20 mL volume
  10. additionA resulted suspension was diluted with EtOAc (20 mL)
  11. filtrationa solid was filtered out
  12. washwashed with EtOAc (20×2)
  13. customdried

Sources & evidence

ORD record
ord-96e87ebc70f640f1b1bfc6683389786e
Source dataset
uspto-grants-2013_12
Patent number
US08598366B2

Reaction notes

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