Hydrogen Peroxide → Tert-butyl 2-methyl-6,7-bis(trifluoromethyl)spiro[3,4-dihydropyrrolo[1,2-a]pyrazine-1,4'-piperidine]-1'-carboxylate

HRID 1405365Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1405365
[CH3:1][N:2]1[C:14]2([CH2:19][CH2:18][N:17]([C:20]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])=[O:21])[CH2:16][CH2:15]2)[C:6]2=[CH:7][CH:8]=[C:9]([C:10]([F:13])([F:12])[F:11])[N:5]2[CH2:4][CH2:3]1.[C:27](I)([F:30])([F:29])[F:28].OO>CS(C)=O>[CH3:1][N:2]1[C:14]2([CH2:19][CH2:18][N:17]([C:20]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])=[O:21])[CH2:16][CH2:15]2)[C:6]2=[CH:7][C:8]([C:27]([F:30])([F:29])[F:28])=[C:9]([C:10]([F:11])([F:13])[F:12])[N:5]2[CH2:4][CH2:3]1

Komponenten

5

Edukt 3

HCID 784Hydrogen PeroxideHCID 16843TrifluoroiodomethaneHCID 68153221tert-Butyl 2'-methyl-6'-(trifluoromethyl)-3',4'-dihydro-2'H-spiro[piperidine-4,1'-pyrrolo[1,2-a]pyrazine]-1-carboxylate

Produkt 1

HCID 86668522Tert-butyl 2-methyl-6,7-bis(trifluoromethyl)spiro[3,4-dihydropyrrolo[1,2-a]pyrazine-1,4'-piperidine]-1'-carboxylate

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 679Dimethyl SulfoxideLösungsmittel

Versuchsvorschrift

Ferrous sulfate heptahydrate (803 μL of 1.00 M, 0.803 mmol) was added to a mixture of tert-butyl 2-methyl-6-(trifluoromethyl)spiro[3,4-dihydropyrrolo[1,2-a]pyrazine-1,4′-piperidine]-1′-carboxylate (1.00 g, 2.68 mmol) and DMSO (15 mL) at room temperature. The vessel was then charged with CF3I (gas) before H2O2 (304 μL of 30% w/v, 2.68 mmol) was added dropwise. The mixture was allowed to stir overnight at room temperature before it was partitioned between ethyl acetate and water. The layers were separated and the aqueous layer was extracted with ethyl acetate (3×). The combined organics were washed with brine, dried over sodium sulfate, filtered and concentrated. The reside was purified by column chromatography (0-100% ethyl acetate/hexanes) to give tert-butyl 2-methyl-6,7-bis(trifluoromethyl)spiro[3,4-dihydropyrrolo[1,2-a]pyrazine-1,4′-piperidine]-1′-carboxylate. ESI-MS m/z calc. 441.2, found 442.5 (M+1)+; Retention time: 1.36 minutes (3 min run).

Aufarbeitung

  1. additionwas added dropwise
  2. customwas partitioned between ethyl acetate and water
  3. customThe layers were separated
  4. extractionthe aqueous layer was extracted with ethyl acetate (3×)
  5. washThe combined organics were washed with brine
  6. dry with materialdried over sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe reside was purified by column chromatography (0-100% ethyl acetate/hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-b1d43d598cea4f2db41dc5bbbbb7e3cc
Quelldatensatz
uspto-grants-2014_12
Patentnummer
US08916565B2

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