Ammonium formate → Methyl 3-hydroxy-5-[(4-methyl-5-oxo-2,3,4,5-tetrahydro-1,4-benzoxazepin-8-yl)oxy]benzoate

HRID 548759Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 548759
Cl[C:2]1[C:12]2[O:11][CH2:10][CH2:9][N:8]([CH3:13])[C:7](=[O:14])[C:6]=2[CH:5]=[CH:4][C:3]=1[O:15][C:16]1[CH:17]=[C:18]([CH:23]=[C:24]([O:26]CC2C=CC=CC=2)[CH:25]=1)[C:19]([O:21][CH3:22])=[O:20].C([O-])=O.[NH4+]>CO.[Pd]>[OH:26][C:24]1[CH:23]=[C:18]([CH:17]=[C:16]([O:15][C:3]2[CH:4]=[CH:5][C:6]3[C:7](=[O:14])[N:8]([CH3:13])[CH2:9][CH2:10][O:11][C:12]=3[CH:2]=2)[CH:25]=1)[C:19]([O:21][CH3:22])=[O:20]

Komponenten

5

Edukt 2

HCID 2723923Ammonium formateHCID 57663169Methyl 3-[(9-chloro-4-methyl-5-oxo-2,3,4,5-tetrahydro-1,4-benzoxazepin-8-yl)oxy]-5-[(phenylmethyl)oxy]benzoate

Produkt 1

HCID 57663229Methyl 3-hydroxy-5-[(4-methyl-5-oxo-2,3,4,5-tetrahydro-1,4-benzoxazepin-8-yl)oxy]benzoateAusbeute 50,4 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 23938PalladiumKatalysatorHCID 887MethanolLösungsmittel

Versuchsvorschrift

A mixture of methyl 3-[(9-chloro-4-methyl-5-oxo-2,3,4,5-tetrahydro-1,4-benzoxazepin-8-yl)oxy]-5-[(phenylmethyl)oxy]benzoate (8.8 g, 18.8 mmol), and ammonium formate (11.87 g, 188 mmol) in methanol (190 mL) was placed under an atmosphere of argon and 10% palladium on charcoal (880 mg) added. The mixture was heated under relux for 2 hours, cooled to RT, filtered through Celite®, washed with methanol, and the filtrates evaporated in vacuo to a residue which was partitioned between water (150 mL) and ethyl acetate (200 mL). The organic layer was washed with brine, dried (MgSO4), evaporated in vacuo to a residue which was chromatographed on basic alumina, eluting with ethyl acetate then methanol, to give a solid which was crystallised from ethyl acetate and isohexane to give the desired compound (3.25 g). 1H NMR δ (CDCl3): 3.15 (s, 3H), 3.5 (t, 2H), 4.35 (t, 2H), 6.6 (dd, 1H), 6.75 (dt, 1H), 7.8 (t, 1H); m/z 344 (M+H)+

Aufarbeitung

  1. temperatureThe mixture was heated under relux for 2 hours
  2. filtrationfiltered through Celite®
  3. washwashed with methanol
  4. customthe filtrates evaporated in vacuo to a residue which
  5. customwas partitioned between water (150 mL) and ethyl acetate (200 mL)
  6. washThe organic layer was washed with brine
  7. dry with materialdried (MgSO4)
  8. customevaporated in vacuo to a residue which
  9. customwas chromatographed on basic alumina
  10. washeluting with ethyl acetate
  11. custommethanol, to give a solid which
  12. customwas crystallised from ethyl acetate and isohexane

Quellen und Nachweise

ORD-Eintrag
ord-b1ee1e035d574a97bb332a0f4ea03e66
Quelldatensatz
uspto-grants-2011_05
Patentnummer
US07943607B2

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