Hydrochloric Acid → (1R)-N-[3-(trifluoromethyl)phenyl]-1,8,8-trimethyl-2,4-dioxobicyclo[3.2.1] octane-3-carboxamide

HRID 349783Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 349783
[CH3:1][C@:2]12[C:9]([CH3:11])([CH3:10])[CH:6]([CH2:7][CH2:8]1)[C:5](=[O:12])[CH2:4][C:3]2=[O:13].C(N(CC)CC)C.[F:21][C:22]([F:33])([F:32])[C:23]1[CH:24]=[C:25]([N:29]=[C:30]=[O:31])[CH:26]=[CH:27][CH:28]=1.Cl>CN(C)C1C=CN=CC=1.ClCCl>[F:21][C:22]([F:32])([F:33])[C:23]1[CH:24]=[C:25]([NH:29][C:30]([CH:4]2[C:5](=[O:12])[CH:6]3[C:9]([CH3:10])([CH3:11])[C@@:2]([CH3:1])([CH2:8][CH2:7]3)[C:3]2=[O:13])=[O:31])[CH:26]=[CH:27][CH:28]=1

Komponenten

7

Edukt 4

HCID 313Hydrochloric AcidHCID 8471TriethylamineHCID 94833-(Trifluoromethyl)phenyl isocyanateHCID 58805524(1R)-1,8,8-trimethylbicyclo[3.2.1]octane-2,4-dione

Produkt 1

HCID 11552369(1R)-N-[3-(trifluoromethyl)phenyl]-1,8,8-trimethyl-2,4-dioxobicyclo[3.2.1] octane-3-carboxamideAusbeute 51,7 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 142844-(Dimethylamino)pyridineKatalysatorHCID 6344DichloromethaneLösungsmittel2×

Reaktionsbedingungen

Temperatur
30 °C

Versuchsvorschrift

To an ice-cooled solution of (1R)-1,8,8-trimethylbicyclo[3.2.1]octane-2,4-dione (0.36 g, 2.0 mmole), triethylamine (0.20 g, 2.0 mmole) and 4-(dimethylamino)pyridine (0.24 g, 2.0 mmole) in dry dichloromethane (25 mL) was added a solution of 3-(trifluoromethyl)phenyl isocyanate (0.37 g, 2.0 mmole) in dry dichloromethane (5 mL). The resulting mixture was allowed to stir overnight under a nitrogen atmosphere, during which time it came up to room temperature, and then was heated at 30° C. for 7 hours. The reaction mixture was treated with 2N aqueous HCl and the layers separated. The acidic aqueous layer was extracted with two additional portions of dichloromethane. The combined organic layers were dried over anhydrous sodium sulfate and concentrated on a rotary evaporator to give a yellow oil, which was purified by chromatography on silica gel (10% ethyl acetate/hexane) to yield a yellow oil, which was crystallized from 95% ethanol to yield the title compound as a beige solid (0.38 g, 51% yield), mp=66–68° C.; MS (−) ESI m/z=366 (M−H)−; [α]D25=+22.0° (c=1, EtOH).

Aufarbeitung

  1. customcame up to room temperature
  2. customthe layers separated
  3. extractionThe acidic aqueous layer was extracted with two additional portions of dichloromethane
  4. dry with materialThe combined organic layers were dried over anhydrous sodium sulfate
  5. concentrationconcentrated on a rotary evaporator
  6. customto give a yellow oil, which
  7. customwas purified by chromatography on silica gel (10% ethyl acetate/hexane)
  8. customto yield a yellow oil, which
  9. customwas crystallized from 95% ethanol

Quellen und Nachweise

ORD-Eintrag
ord-a8d964f10924456481fa7db7a6ff12ae
Quelldatensatz
uspto-grants-2007_02
Patentnummer
US07179943B2

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