Methanesulfonic acid 1-(3-benzyloxy-1-methyl-4-oxo-1,4-dihydro-pyridin-2-yl)-2,2,2-trifluoro-ethyl ester → 3-Hydroxy-1-methyl-2-(2,2,2-trifluoroethyl)-4(1H)-pyridinone

HRID 913014Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 913014
C([O:8][C:9]1[C:14](=[O:15])[CH:13]=[CH:12][N:11]([CH3:16])[C:10]=1[CH:17](OS(C)(=O)=O)[C:18]([F:21])([F:20])[F:19])C1C=CC=CC=1.[H][H]>C(O)C.[Pd]>[OH:8][C:9]1[C:14](=[O:15])[CH:13]=[CH:12][N:11]([CH3:16])[C:10]=1[CH2:17][C:18]([F:21])([F:19])[F:20]

Komponenten

5

Edukt 2

HCID 86623501Methanesulfonic acid 1-(3-benzyloxy-1-methyl-4-oxo-1,4-dihydro-pyridin-2-yl)-2,2,2-trifluoro-ethyl esterHCID 178418361HCID 178418361, Verbindung

Produkt 1

HCID 249445483-Hydroxy-1-methyl-2-(2,2,2-trifluoroethyl)-4(1H)-pyridinoneAusbeute 9,7 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 23938PalladiumKatalysatorHCID 702EthanolLösungsmittel

Versuchsvorschrift

A mixture of methanesulfonic acid 1-(3-benzyloxy-1-methyl-4-oxo-1,4-dihydro-pyridin-2-yl)-2,2,2-trifluoro-ethyl ester (2.80 g, 7.15 mmol) and 10% Pd/C (0.56 g) in ethyl alcohol was subjected to hydrogenation in a Parr apparatus under 50 psi hydrogen pressure for 90 min. The mixture was filtered through a pad of CELITE™, and the filtrate was concentrated to dryness. The residue was purified by flash column chromatography on silica gel using a mixture of isopropyl alcohol and a conc. NH4OH solution (90/10, v/v) as eluant. Fractions rich in the product were pooled together and evaporated to dryness, thereby affording 3-hydroxy-1-methyl-2-(2,2,2-trifluoro-ethyl)-1H-pyridin-4-one (first crop: 143 mg, 9.7% yield, second crop: 240 mg, 16.2% yield). 1H NMR (90 MHz, CD3OD) δ (ppm): 7.66 (d, J=7.2 Hz, 1H), 6.41 (d, J=7.4 Hz, 1H), 3.89 (q, J=10.2 Hz, 1H) and 3.82 (s, 3H); MS-ESI (m/z): 208 [M+1]+, 188.2, 168.2. HPLC purity (peak area percent) of both fractions are about 98% at λ=254 nm, RT=3.75 min (HPLC method is described in Part A above).

Aufarbeitung

  1. filtrationThe mixture was filtered through a pad of CELITE™
  2. concentrationthe filtrate was concentrated to dryness
  3. customThe residue was purified by flash column chromatography on silica gel using
  4. additiona mixture of isopropyl alcohol
  5. customevaporated to dryness

Quellen und Nachweise

ORD-Eintrag
ord-6c374bf63c384fe3a68701585941733d
Quelldatensatz
uspto-grants-2011_09
Patentnummer
US08026261B2

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