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

HRID 1625938노트

반응식

HRID 1625938 반응식
Cl.[CH2:2]1[C:7]2([CH2:12][CH2:11][N:10]([C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH2:9][CH2:8]2)[CH2:6][NH:5][CH2:4][CH2:3]1.C(=O)([O-])[O-].[Cs+].[Cs+].Br[CH2:27][CH2:28][C:29]#[CH:30]>C(#N)C>[CH2:30]([N:5]1[CH2:6][C:7]2([CH2:8][CH2:9][N:10]([C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH2:11][CH2:12]2)[CH2:2][CH2:3][CH2:4]1)[CH2:29][C:28]#[CH:27]

참가 물질

5

반응물 3

HCID 10796Cesium carbonateHCID 110734644-Bromobut-1-yne2회HCID 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 72%

시약·촉매·용매 1

HCID 6342Acetonitrile용매

반응 조건

온도
60 °C

실험 절차

A mixture of tert-butyl 4,9-diazaspiro[5.5]undecane-9-carboxylate hydrochloride (170.00 g, 584.53 mmoles), cesium carbonate (476.13 g, 1.46 moles), and 4-bromobutyne (93.28 g, 701.43 mmoles) in acetonitrile (1.70 L) is heated to 60° C. and stirred at this temperature overnight. Further 4-bromobutyne (46.64 g, 350.72 mmoles) is added and the mixture is stirred at 60° C. overnight. The mixture is cooled and filtered. The filtrate is concentrated under reduced pressure and the residue dissolved in ethyl acetate (500 mL), washed with water (1 L), and saturated aqueous sodium chloride (1 L), then dried over MgSO4, and filtered. The filtrate is concentrated under reduced pressure and the residue is purified by silica column chromatography eluting with 20 to 70% ethyl acetate in dichloromethane to provide the title compound (129 g, 72% yield). Mass spectrum (m/z): 307.25 (M+1).

후처리

  1. stirringthe mixture is stirred at 60° C. overnight
  2. temperatureThe mixture is cooled
  3. filtrationfiltered
  4. concentrationThe filtrate is concentrated under reduced pressure
  5. dissolutionthe residue dissolved in ethyl acetate (500 mL)
  6. washwashed with water (1 L), and saturated aqueous sodium chloride (1 L)
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. concentrationThe filtrate is concentrated under reduced pressure
  10. customthe residue is purified by silica column chromatography
  11. washeluting with 20 to 70% ethyl acetate in dichloromethane

출처 및 근거

ORD 기록
ord-2bad867ee657407b94547cbb3190a8a3
출처 데이터셋
uspto-grants-2014_07
특허 번호
US08785404B2

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