2-Bromopyridine → HCID 66875697、化合物

HRID 1666513ノート

反応式

HRID 1666513 の反応式
[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]

参加物

6

反応物 3

HCID 79732-Bromopyridine2 回HCID 10796Cesium carbonateHCID 53485958Tert-butyl 4-(3-hydroxybenzylidene)piperidine-1-carboxylate

生成物 1

HCID 66875697HCID 66875697、化合物収率 76%

試薬・触媒・溶媒 2

HCID 11068737tetrakis(acetonitrile)copper(I) hexafluorophosphate触媒2 回HCID 1140Toluene溶媒

実験手順

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.).

後処理

  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

出典と根拠

ORDレコード
ord-d99cf0255f4b4dc0837427e92d72a689
出典データセット
uspto-grants-2011_10
特許番号
US08044052B2

反応ノート

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