Ethanol → ethyl 6-[(hydroxyimino)methyl]-2-(trifluoromethyl)-2H-1-benzopyran-3-carboxylate

HRID 722307Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 722307
Cl.[NH2:2][OH:3].[CH:4]([C:6]1[CH:7]=[CH:8][C:9]2[O:14][CH:13]([C:15]([F:18])([F:17])[F:16])[C:12]([C:19]([O:21][CH2:22][CH3:23])=[O:20])=[CH:11][C:10]=2[CH:24]=1)=O.C([O-])(=O)C.[Na+].C(O)C>O.C(OCC)C>[OH:3][N:2]=[CH:4][C:6]1[CH:7]=[CH:8][C:9]2[O:14][CH:13]([C:15]([F:18])([F:17])[F:16])[C:12]([C:19]([O:21][CH2:22][CH3:23])=[O:20])=[CH:11][C:10]=2[CH:24]=1

Komponenten

7

Edukt 4

HCID 702EthanolHCID 443297Hydroxyamine hydrochlorideHCID 517045Sodium AcetateHCID 21883688ethyl 6-formyl-2-(trifluoromethyl)-2H-1-benzopyran-3-carboxylate

Produkt 1

HCID 73852042ethyl 6-[(hydroxyimino)methyl]-2-(trifluoromethyl)-2H-1-benzopyran-3-carboxylateAusbeute 55 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 962WaterLösungsmittel2×HCID 3283Diethyl EtherLösungsmittel

Versuchsvorschrift

A 50 mL round bottom flask was charged with hydroxylamine HCl (0.255 g, 3.67 mmol), ethyl 6-formyl-2-(trifluoromethyl)-2H-1-benzopyran-3-carboxylate (Example 75, Step 1) (1.00 g, 3.34 mmol), sodium acetate (0.301 g, 3.67 mmol), ethanol (10 mL), and H2O (2 mL). The reaction was stirred at room temperature for 18 hours, then diluted with H2O and diethyl ether. The layers were separated and the organic phase washed with H2O, brine, dried over MgSO4, filtered, and concentrated in vacuo yielding an orange semi-crystalline mass. Recrystallization of this solid from hot ethyl acetate and isooctane yielded the oxime (0.578 g, 55%): mp 113.0–116.2° C. 1H NMR (acetone-d6/300 MHz) 10.46 (s, ca.1 exch.), 8.11 (s, 2H), 7.92 (s, 1H), 7.72 (d, 1H, J=2 Hz)), 7.68 (dd, 1H, J=8.5, 2.0 Hz), 7.07 (d, 1H, J=8.5 Hz), 5.89 (q, 1H, J=7.1 Hz), 4.43−4.22 (m, 2H), 1.34 9t, 3H, J=7.3 Hz). FABLRMS m/z 316 (M+H). EIHRMS m/z 315.0719 (M+, Calc'd 315.0733). Anal. Calc'd for C14H12F3N1O4: C, 53.34; H, 3.84; N 4.44. Found: C, 53.85; H, 3.90; N, 4.19.

Aufarbeitung

  1. customThe layers were separated
  2. washthe organic phase washed with H2O, brine
  3. dry with materialdried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customyielding an orange semi-crystalline mass
  7. customRecrystallization of this solid from hot ethyl acetate and isooctane

Quellen und Nachweise

ORD-Eintrag
ord-54ba110f70484f6aa98b3300006c61d5
Quelldatensatz
uspto-grants-2006_11
Patentnummer
US07138411B2

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