Dimethylformamide → Ethyl 1-benzyl-3-methyl-4-oxopiperidine-3-carboxylate

HRID 80848ノート

反応式

HRID 80848 の反応式
Cl.[CH2:2]([N:9]1[CH2:14][CH2:13][C:12](=[O:15])[CH:11]([C:16]([O:18][CH2:19][CH3:20])=[O:17])[CH2:10]1)[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.[CH3:21]N(C=O)C.[OH-].[K+].IC>C1COCC1>[CH2:2]([N:9]1[CH2:14][CH2:13][C:12](=[O:15])[C:11]([CH3:21])([C:16]([O:18][CH2:19][CH3:20])=[O:17])[CH2:10]1)[C:3]1[CH:4]=[CH:5][CH:6]=[CH:7][CH:8]=1

参加物

6

反応物 4

HCID 6228DimethylformamideHCID 6328Methyl iodideHCID 14797Potassium HydroxideHCID 102623Ethyl 1-benzyl-4-oxopiperidine-3-carboxylate hydrochloride

生成物 1

HCID 14666544Ethyl 1-benzyl-3-methyl-4-oxopiperidine-3-carboxylate

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

To a suspension of ethyl 1-benzyl-4-oxopiperidine-3-carboxylate hydrochloride (20 g, 67.2 mmol) in THF (130 mL)/DMF (130 mL) was added KOH (powder, 7.64 g, 136 mmol) at room temperature. The reaction mixture was stirred for 5-10 min, then added iodomethane (4.62 mL, 73.9 mmol) dropwise. The reaction mixture was further stirred for 3 h at room temperature and then quenched with water. The aqueous phase was extracted with diethyl ether twice. The organic phases were combined and washed with water, dried over Na2SO4, filtered and concentrated. The resulting residue was purified by silica gel flash chromatography (0-20% EtOAc/heptanes) to provide ethyl 1-benzyl-3-methyl-4-oxopiperidine-3-carboxylate. 1H NMR (400 MHz, DMSO-d6) δ ppm 7.15-7.45 (m, 5H), 4.00-4.21 (m, 2H), 3.66 (d, J=13.39 Hz, 1H), 3.47 (d, J=13.39 Hz, 1H), 3.30 (dd, J=2.78, 11.62 Hz, 1H), 2.96-3.08 (m, 1H), 2.77 (ddd, J=6.69, 11.68, 14.46 Hz, 1H), 2.36-2.45 (m, 1H), 2.27-2.35 (m, 1H), 2.14 (d, J=11.37 Hz, 1H), 1.15 (t, J=7.07 Hz, 3H), 1.09 (s, 3H).

後処理

  1. stirringThe reaction mixture was further stirred for 3 h at room temperature
  2. customquenched with water
  3. extractionThe aqueous phase was extracted with diethyl ether twice
  4. washwashed with water
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe resulting residue was purified by silica gel flash chromatography (0-20% EtOAc/heptanes)

出典と根拠

ORDレコード
ord-6279ed0557b14bc58f220b1ef01c0a2d
出典データセット
uspto-grants-2014_09
特許番号
US08846656B2

反応ノート

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