2-Bromopyridine → HCID 66875697, 화합물

HRID 1666513노트

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HRID 1666513 반응식
[OH:1][C:2]1[CH:3]=[C:4]([CH:19]=[CH:20][CH:21]=1)[CH:5]=[C:6]1[CH2:11][CH2:10][N:9]([C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])[CH2:8][CH2:7]1.Br[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][N:24]=1.C(=O)([O-])[O-].[Cs+].[Cs+]>C1(C)C=CC=CC=1.CC#N.CC#N.CC#N.CC#N.F[P-](F)(F)(F)(F)F.[Cu+]>[C:15]([O:14][C:12]([N:9]1[CH2:8][CH2:7][C:6](=[CH:5][C:4]2[CH:19]=[CH:20][CH:21]=[C:2]([O:1][C:23]3[CH:28]=[CH:27][CH:26]=[CH:25][N:24]=3)[CH:3]=2)[CH2:11][CH2:10]1)=[O:13])([CH3:18])([CH3:16])[CH3:17]

참가 물질

6

반응물 3

HCID 79732-Bromopyridine2회HCID 10796Cesium carbonateHCID 53485958Tert-butyl 4-(3-hydroxybenzylidene)piperidine-1-carboxylate

생성물 1

HCID 66875697HCID 66875697, 화합물수율 76%

시약·촉매·용매 2

HCID 11068737tetrakis(acetonitrile)copper(I) hexafluorophosphate촉매2회HCID 1140Toluene용매

실험 절차

A mixture of tert-butyl 4-(3-hydroxybenzylidene)piperidine-1-carboxylate (0.300 g, Example 57, Step 3), 2-bromopyridine (0.253 mL, 1.50 equiv), cesium carbonate (1.13 g, 2.01 equiv), and tetrakis(acetonitrile)copper(I) hexafluorophosphate (0.048 g, 0.075 equiv) in toluene (9 mL, 0.2 M) was heated to reflux for 12 hours. Additional tetrakis(acetonitrile)copper(I) hexafluorophosphate (0.02 g) and 2-bromopyridine (0.1 mL) were added, and the reaction was heated an additional 6 hours. After cooling to room temperature, the reaction was filtered through Celite, washing the Celite with dichloromethane. The filtrate was concentrated and purified on 60 g silica gel using a gradient eluent consisting of 0-10% ethyl acetate/dichloromethane over 60 minutes to give the title compound as a white solid. 0.483 g, 76% yield. 1H NMR (400 MHz, CDCl3) δ ppm 1.45 (9H, s), 2.29 (2H, br. S.), 2.45 (2H, t, J=5.5 Hz), 3.37 (2H, t, J=5.4 Hz), 3.47 (2H, t, J=5.7 Hz), 6.32 (1H, s), 6.76-7.13 (5H, m), 7.32 (1H, t, J=7.7 Hz), 7.67 (1H, t, J=6.5 Hz), 8.18 (1H, br. s.).

후처리

  1. temperaturewas heated
  2. temperatureto reflux for 12 hours
  3. temperaturethe reaction was heated an additional 6 hours
  4. filtrationthe reaction was filtered through Celite
  5. washwashing the Celite with dichloromethane
  6. concentrationThe filtrate was concentrated
  7. custompurified on 60 g silica gel using a gradient eluent

출처 및 근거

ORD 기록
ord-d99cf0255f4b4dc0837427e92d72a689
출처 데이터셋
uspto-grants-2011_10
특허 번호
US08044052B2

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