Dimethylformamide → HCID 15425895, Verbindung

HRID 1043974Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1043974
FC(F)(F)S(O[C:7]1[CH:8]=[CH:9][C:10]2[CH2:11][C@H:12]3[N:24]([CH2:25][CH:26]4[CH2:28][CH2:27]4)[CH2:23][CH2:22][C@:18]45[C:19]=2[C:20]=1[O:21][C@H:17]4[C:16](=[O:29])[CH2:15][CH2:14][C@@:13]35[OH:30])(=O)=O.[CH3:33][N:34](C=O)C>C(OCC)(=O)C.[C-]#N.[Zn+2].[C-]#N.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH:26]1([CH2:25][N:24]2[CH2:23][CH2:22][C@:18]34[C:19]5[C:20]6[O:21][C@H:17]3[C:16](=[O:29])[CH2:15][CH2:14][C@@:13]4([OH:30])[C@H:12]2[CH2:11][C:10]=5[CH:9]=[CH:8][C:7]=6[C:33]#[N:34])[CH2:27][CH2:28]1

Komponenten

6

Edukt 2

HCID 6228DimethylformamideHCID 15425894Morphinan-?6-?one, 17-?(cyclopropylmethyl)?-?4,?5-?epoxy-?14-?hydroxy-?3-?[[(trifluoromethyl)?sulfonyl]?oxy]?-?, (5α)?-

Produkt 1

HCID 15425895HCID 15425895, VerbindungAusbeute 61 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 11186Zinc cyanide (Zn(CN)2)KatalysatorHCID 178418397HCID 178418397, VerbindungKatalysatorHCID 8857Ethyl AcetateLösungsmittel

Reaktionsbedingungen

Temperatur
120 °C

Versuchsvorschrift

A mixture of (5a)-17-(cyclopropylmethyl)-14-hydroxy-6-oxo-4,5-epoxymorphinan-3-yl trifluoromethanesulfonate [P1](38.0 g, 80.3 mmol), zinc cyanide (18.85 g, 160.5 mmol), and tetrakis(triphenylphosphine)palladium(0) (8.5 g, 7.36 mmol) in DMF (500 mL—degassed with argon for 3 hours) was heated at 120° C. under argon for 3 hours. The reaction mixture was allowed to return to room temperature then diluted with ethyl acetate (1 L) and passed through a pad of celite. The solution was washed with water (3×1 L) and the organic phase dried (MgSO4). Filtration and removal of the solvent under reduced pressure gave crude product that was triturated with methanol to give (5a)-17-(cyclopropylmethyl)-14-hydroxy-6-oxo-4,5-epoxymorphinan-3-carbonitrile [P2] (17.12 g, 61% yield); LC/MS (r.t. 12.7 minutes [5 to 95% B]), 351 (M+H)+.

Aufarbeitung

  1. customto return to room temperature
  2. washThe solution was washed with water (3×1 L)
  3. dry with materialthe organic phase dried (MgSO4)
  4. filtrationFiltration and removal of the solvent under reduced pressure
  5. customgave crude product that
  6. customwas triturated with methanol

Quellen und Nachweise

ORD-Eintrag
ord-dc383890e0284ab8aef3b20e5331dad6
Quelldatensatz
uspto-grants-2013_10
Patentnummer
US08563572B2

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