Potassium Sodium Tartrate → 1-Oxo-3-(4-trifluoromethyl-phenyl)-1,2-dihydro-pyrrolo[1,2-a]pyrazine-6-carbaldehyde

HRID 77361Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 77361
[O:1]=[C:2]1[NH:7][C:6]([C:8]2[CH:13]=[CH:12][C:11]([C:14]([F:17])([F:16])[F:15])=[CH:10][CH:9]=2)=[CH:5][N:4]2[C:18]([C:21]#N)=[CH:19][CH:20]=[C:3]12.[H-].C([Al+]CC(C)C)C(C)C.[C@H](O)(C([O-])=O)[C@@H](O)C([O-])=[O:36].[Na+].[K+]>C(Cl)Cl>[O:1]=[C:2]1[NH:7][C:6]([C:8]2[CH:13]=[CH:12][C:11]([C:14]([F:15])([F:17])[F:16])=[CH:10][CH:9]=2)=[CH:5][N:4]2[C:18]([CH:21]=[O:36])=[CH:19][CH:20]=[C:3]12

Komponenten

5

Edukt 3

HCID 9357Potassium Sodium TartrateHCID 21225700Diisobutylaluminumhydride2×HCID 727149431-Oxo-3-(4-trifluoromethyl-phenyl)-1,2-dihydro-pyrrolo[1,2-a]pyrazine-6-carbonitrile

Produkt 1

HCID 867066601-Oxo-3-(4-trifluoromethyl-phenyl)-1,2-dihydro-pyrrolo[1,2-a]pyrazine-6-carbaldehydeAusbeute 40 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel3×

Reaktionsbedingungen

Temperatur
-75 °C

Versuchsvorschrift

A mixture of 1-oxo-3-(4-trifluoromethyl-phenyl)-1,2-dihydro-pyrrolo[1,2-a]pyrazine-6-carbonitrile (Example 2) (55 mg, 0.18 mmol) in methylene chloride (1 mL) cooled −75° C. was treated dropwise with 1M diisobutylaluminum hydride in methylene chloride (275 μL, 0.27 mmol). The reaction was stirred at −75° C. for 1.5 h. At this time, the reaction was treated with additional 1M diisobutylaluminum hydride in methylene chloride (0.1 mL, 0.1 mmol) and allowed to stir at −75° C. for an additional 1 h. At this time, the reaction was treated with a solution of Rochelle's salt, and the mixture was allowed to warm up to room temperature where it stirred overnight. At this time, the resulting suspension was absorbed onto silica gel. Flash chromatography (4 g silica column, 0-50% ethyl acetate/hexanes) afforded 1-oxo-3-(4-trifluoromethyl-phenyl)-1,2-dihydro-pyrrolo[1,2-a]pyrazine-6-carbaldehyde (22 mg, 40%) as light yellow solid. 1H NMR (acetone-d6) δ ppm 10.02 (s, 1H), 8.11 (d, J=1.5 Hz, 1H), 8.03 (d, J=8.0 Hz, 2H), 7.89 (d, J=8.5 Hz, 2H), 7.85 (s, 1H), 7.42 (s, 1H). LC-MS calcd. for C15H10F3N2O2 [(M+H)+] 307, obsd. 306.8.

Aufarbeitung

  1. stirringto stir at −75° C. for an additional 1 h
  2. temperatureto warm up to room temperature where it
  3. stirringstirred overnight
  4. customAt this time, the resulting suspension was absorbed onto silica gel

Quellen und Nachweise

ORD-Eintrag
ord-7a36bf40573e4080b19c075ef0998172
Quelldatensatz
uspto-grants-2014_09
Patentnummer
US08841299B2

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