Tetrafluoroboric acid → HCID 42639483, Verbindung

HRID 1351396Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1351396
[F:1][C:2]1[CH:7]=[CH:6][C:5]([C@@H:8]2[C@@H:13]([OH:14])[CH2:12][CH2:11][C@H:10]([C:15]([O:17][CH2:18][CH3:19])=[O:16])[C@H:9]2[C:20]([O:22][CH2:23][CH3:24])=[O:21])=[CH:4][CH:3]=1.[F:25][C:26]([F:47])([F:46])[C:27]1[CH:28]=[C:29]([C@@H:37](OC(=N)C(Cl)(Cl)Cl)[CH3:38])[CH:30]=[C:31]([C:33]([F:36])([F:35])[F:34])[CH:32]=1.[H+].[B-](F)(F)(F)F>CCOCC>[F:25][C:26]([F:46])([F:47])[C:27]1[CH:28]=[C:29]([C@H:37]([O:14][C@H:13]2[CH2:12][CH2:11][C@H:10]([C:15]([O:17][CH2:18][CH3:19])=[O:16])[C@@H:9]([C:20]([O:22][CH2:23][CH3:24])=[O:21])[C@@H:8]2[C:5]2[CH:4]=[CH:3][C:2]([F:1])=[CH:7][CH:6]=2)[CH3:38])[CH:30]=[C:31]([C:33]([F:34])([F:35])[F:36])[CH:32]=1

Komponenten

5

Edukt 3

HCID 28118Tetrafluoroboric acidHCID 11611082Trichloroacetimidic acid (S)-1-[3,5-bis(trifluoromethyl)phenyl]ethyl esterHCID 42639482(1S,2S,3R,4S)-diethyl 3-(4-fluorophenyl)-4-hydroxycyclohexane-1,2-dicarboxylate

Produkt 1

HCID 42639483HCID 42639483, VerbindungAusbeute 59,1 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 3283Diethyl EtherLösungsmittel2×

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

To a solution of 9.09 g (26.9 mmol) of the first eluting isomer diethyl (1S,2S,3R,4S)-3-(4-fluorophenyl)-4-hydroxycyclohexane-1,2-dicarboxylate (step D) and 21.5 g (53.5 mmol) of (1S)-1-[3,5-bis(trifluoromethyl)phenyl]ethyl-2,2,2-trichloroethanimidoate (step E) in 250 mL of cyclohexane/1,2chloroethane (3/1) under nitrogen atmosphere at −5° C. was added 0.51 mL (3.58 mmol) of 54% HBF4 in ether. The reaction mixture was stirred at −5° C. to at 0° C. for 2 hr then diluted with ether. The mixture was washed with sat. aq. NaHCO3. The organic layer was dried over drying agent, filtered and the solvent evaporated under vacuum. The residue was purified by flash column chromatography on silica gel eluting with EtOAc/hexanes (1/4) to give 9.2 g of the title compound as an oil. 1H-NMR (CDCl3): δ: δ: 7.70 (1H, s), 7.20 (2H, s), 7.00 (2H, m), 6.85 (2H, t, J=8.5 Hz), 4.43 (1H, q, J=6.0 Hz), 4.20–4.10 (2H, m), 3.80–3.73 (2H, m), 3.36 (1H, m), 2.90–2.76 (2H, m), 2.40 (1H, m), 2.28 (1H, m), 1.63–1.55 (2H, m), 1.33 (3H, d, J=6.0 Hz), 1.25 (3H, t, J=7.2 Hz), 0.82 (3H, t, J=7.2 Hz). Unreacted starting alcohol could be recovered by flushing the column with EtOAc and reused in the above reaction.

Aufarbeitung

  1. washThe mixture was washed with sat. aq. NaHCO3
  2. customThe organic layer was dried
  3. customover drying agent
  4. filtrationfiltered
  5. customthe solvent evaporated under vacuum
  6. customThe residue was purified by flash column chromatography on silica gel eluting with EtOAc/hexanes (1/4)

Quellen und Nachweise

ORD-Eintrag
ord-3a1980f07d4e47978c83e70de6ee95ad
Quelldatensatz
uspto-grants-2007_05
Patentnummer
US07217731B2

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