Dimethylformamide → 4-(Isocyano(tosyl)methyl)-1-tosylpiperidine

HRID 1616343ノート

反応式

HRID 1616343 の反応式
[H-].[Na+].[C:3]1(C)[C:4]([S:9]([CH2:12][N+:13]#[C-:14])(=[O:11])=[O:10])=[CH:5][CH:6]=[CH:7][CH:8]=1.Br[CH:17]1[CH2:22][CH2:21][N:20]([S:23]([C:26]2[CH:32]=[CH:31][C:29]([CH3:30])=[CH:28][CH:27]=2)(=[O:25])=[O:24])[CH2:19][CH2:18]1.[CH3:33]N(C=O)C>C(OCC)(=O)C.[Li+].[Cl-]>[N+:13]([CH:12]([S:9]([C:4]1[CH:3]=[CH:8][C:7]([CH3:33])=[CH:6][CH:5]=1)(=[O:10])=[O:11])[CH:17]1[CH2:22][CH2:21][N:20]([S:23]([C:26]2[CH:32]=[CH:31][C:29]([CH3:30])=[CH:28][CH:27]=2)(=[O:25])=[O:24])[CH2:19][CH2:18]1)#[C-:14]

参加物

7

反応物 4

HCID 6228Dimethylformamide3 回HCID 24758Sodium hydrideHCID 113590324-Bromo-1-tosylpiperidineHCID 53627694Toluenesulfonylmethyl isocyanide

生成物 1

HCID 595655894-(Isocyano(tosyl)methyl)-1-tosylpiperidine

試薬・触媒・溶媒 2

HCID 8857Ethyl Acetate溶媒HCID 433294Lithium Chloride溶媒

実験手順

NaH (0.92 g, 23.07 mmol, 60% dispersion in oil) was added to DMF (70 mL) in one portion at 0° C. Toluenesulphonylmethyl isocyanide (3.0 g, 15.38 mmol) in DMF (12 mL) was added dropwise over 5 minutes and the mixture was stirred while warming to r.t. for 20 minutes. 4-Bromo-1-tosylpiperidine (4.46 g, 18.4 mmol) in DMF (10 mL) was then added dropwise over 3 minutes and the resulting mixture was stirred at r.t. for 16 h. The mixture was then diluted with ethyl acetate (250 mL) and LiCl (1 M aqueous solution, 60 mL), and the separated organic layer was washed with water (60 mL), dried over MgSO4, filtered and concentrated under reduced pressure. The residue was purified by flash chromatography (20% EtOAc/hexane) to provide 4-(isocyano(tosyl)methyl)-1-tosylpiperidine as a white solid: 1H NMR (400 MHz, CDCl3) δ 7.79 (d, J=8.0 Hz, 2H), 7.61 (d, J=7.6 Hz, 2H), 7.38 (d, J=8.0 Hz, 2H), 7.32 (d, J=7.6 Hz, 2H), 4.34 (d, J=4.0 Hz, 1H), 3.87-3.84 (m, 2H), 2.44 (s, 3H), 2.43 (s, 3H), 2.30-2.10 (m, 2H), 2.10-2.0 (m, 1H), 2.0-1.70 (m, 4H); MS (ESI) 451.1 (M+H+H2O)+.

後処理

  1. stirringthe resulting mixture was stirred at r.t. for 16 h
  2. washthe separated organic layer was washed with water (60 mL)
  3. dry with materialdried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure
  6. customThe residue was purified by flash chromatography (20% EtOAc/hexane)

出典と根拠

ORDレコード
ord-920f63ab00e24992900f4b6506c972fc
出典データセット
uspto-grants-2014_07
特許番号
US08765788B2

反応ノート

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