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

HRID 1616343노트

반응식

HRID 1616343 반응식
[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]

참가 물질

7

반응물 4

HCID 6228Dimethylformamide3회HCID 24758Sodium hydrideHCID 113590324-Bromo-1-tosylpiperidineHCID 53627694Toluenesulfonylmethyl isocyanide

생성물 1

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

시약·촉매·용매 2

HCID 8857Ethyl Acetate용매HCID 433294Lithium Chloride용매

실험 절차

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)+.

후처리

  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)

출처 및 근거

ORD 기록
ord-920f63ab00e24992900f4b6506c972fc
출처 데이터셋
uspto-grants-2014_07
특허 번호
US08765788B2

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