Cesium carbonate → tert-Butyl 2-(but-3-yn-1-yl)-2,9-diazaspiro[5.5]undecane-9-carboxylate

HRID 931679Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 931679
C(=O)([O-])[O-].[Cs+].[Cs+].Cl.[CH2:8]1[C:13]2([CH2:18][CH2:17][N:16]([C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[CH2:15][CH2:14]2)[CH2:12][NH:11][CH2:10][CH2:9]1.Br[CH2:27][CH2:28][C:29]#[CH:30]>C(#N)C>[CH2:30]([N:11]1[CH2:12][C:13]2([CH2:14][CH2:15][N:16]([C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[CH2:17][CH2:18]2)[CH2:8][CH2:9][CH2:10]1)[CH2:29][C:28]#[CH:27]

Komponenten

5

Edukt 3

HCID 10796Cesium carbonateHCID 110734644-Bromobut-1-yneHCID 71464197Tert-butyl 2,9-diazaspiro[5.5]undecane-9-carboxylate hydrochloride

Produkt 1

HCID 86701859tert-Butyl 2-(but-3-yn-1-yl)-2,9-diazaspiro[5.5]undecane-9-carboxylateAusbeute 98 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6342AcetonitrileLösungsmittel

Versuchsvorschrift

Cesium carbonate (46.66 g, 143.21 mmol) is added to a suspension of tert-butyl 4,9-diazaspiro[5.5]undecane-9-carboxylate hydrochloride (16.66 g, 57.28 mmoles) in acetonitrile (167 mL). The mixture is stirred for 10 minutes at ambient temperature then 4-bromobutyne (6.45 mL, 68.74 mmol) is added. The reaction is heated to reflux and stirred for 18 hours. The mixture is cooled and concentrated under reduced pressure. The residue is partitioned between water (200 mL) and ethyl acetate (150 mL). The phases are separated and the aqueous layer is extracted with ethyl acetate (100 mL). The combined organic layers are washed with water (200 mL), then brine (150 mL), dried over MgSO4, filtered, and concentrated under reduced pressure to give the title compound (17.2 g, 98% yield). 1H NMR (300.11 MHz, CDCl3): δ 3.43-3.31 (m, 4H), 2.53-2.48 (m, 2H), 2.37-2.29 (m, 4H), 2.20 (s, 2H), 1.94 (t, J=2.6 Hz, 1H), 1.44 (s, 17H).

Aufarbeitung

  1. temperatureThe reaction is heated
  2. temperatureto reflux
  3. stirringstirred for 18 hours
  4. temperatureThe mixture is cooled
  5. concentrationconcentrated under reduced pressure
  6. customThe residue is partitioned between water (200 mL) and ethyl acetate (150 mL)
  7. customThe phases are separated
  8. extractionthe aqueous layer is extracted with ethyl acetate (100 mL)
  9. washThe combined organic layers are washed with water (200 mL)
  10. dry with materialbrine (150 mL), dried over MgSO4
  11. filtrationfiltered
  12. concentrationconcentrated under reduced pressure

Quellen und Nachweise

ORD-Eintrag
ord-bdb5074e98814107907c51c3bc955b07
Quelldatensatz
uspto-grants-2016_03
Patentnummer
US09296775B2

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