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

HRID 2366516노트

반응식

HRID 2366516 반응식
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]

참가 물질

5

반응물 3

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

생성물 1

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

시약·촉매·용매 1

HCID 6342Acetonitrile용매

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-1a43b68cb04f4d13a829944c1ab65160
출처 데이터셋
uspto-grants-2014_04
특허 번호
US08697849B2

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