Diethyl Ether → 4-(3-Methoxyphenyl)butanenitrile

HRID 2258567노트

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HRID 2258567 반응식
[C-:1]#[N:2].[Na+].[CH3:4][O:5][C:6]1[CH:7]=[C:8]([CH2:12][CH2:13][CH2:14]I)[CH:9]=[CH:10][CH:11]=1.C(OCC)C>CS(C)=O>[CH3:4][O:5][C:6]1[CH:7]=[C:8]([CH2:12][CH2:13][CH2:14][C:1]#[N:2])[CH:9]=[CH:10][CH:11]=1

참가 물질

5

반응물 3

HCID 3283Diethyl EtherHCID 8929Sodium CyanideHCID 127653893-(3-Methoxyphenyl)propyl iodide

생성물 1

HCID 5789544-(3-Methoxyphenyl)butanenitrile

시약·촉매·용매 1

HCID 679Dimethyl Sulfoxide용매

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온도
90 °C

실험 절차

A magnetically stirred suspension of sodium cyanide (13.65 g, 265 mmol) in anhydrous methyl sulfoxide (65 mL) was treated dropwise with 3-(3-methoxyphenyl)propyl iodide (66.25 g, 240 mmol) at a rate sufficient to keep the temperature below 45° C. The suspension was heated at 90° C. for 1 h, cooled to room temperature, poured over ice (1000 g), treated with diethyl ether (500 mL), the layers separated, and the aqueous portion back-extracted with diethyl ether (2×300 mL). The combined organic extracts were washed with water (3×500 mL), 6N HCl (500 mL), brine (500 mL), dried (MgSO4), filtered, and concentrated in vacuo to a clear liquid. Kugelrohr distillation (0.1 torr, 120° C.) provided the desired product as a dear liquid (37.62 g, 89%): 1H NMR (CDCl3) δ7.25 (t, J=8 Hz, 1H), 6.78-6.69 (m, 3 H), 3.80 (s, 3 H), 2.75 (t, J=8 Hz, 2 H), 2.31 (t, J=8 Hz, 2 H), 1.98 (quint, J=8 Hz, 2 H). 4-(3-Methoxyphenyl)butylamine: To a Parr bottle flushed with nitrogen was added -1.0 g of Raney Nickel (50% suspension in H2O), ethanol (125 mL), ammonium hydroxide (30 mL), and a solution of 4-(3-methoxyphenyl)butyronitrile (8.49 g, 48.4 mmol) in ethanol (150 mL). The bottle was charged with hydrogen (60 psi) and rocked 3 d. The suspension was filtered through Celite, the cake rinsed with fresh ethanol (400 mL), and the combined filtrate concentrated in vacuo. The resulting suspension was treated with dichloromethane (200 mL) and water (200 mL), the layers separated, and the aqueous portion back-extracted with fresh dichloromethane (2×150 mL). The combined organic portions were washed with saturated sodium chloride solution (300 mL), dried (K2CO3), filtered, and concentrated in vacuo. Kugelrohr distillation (0.1 torr, 120° C.) provided the desired product as a dear liquid (6.77 g, 78%) which was identical spectroscopically to that previously reported. Venit, J. J.; DiPierro, M.; Magnus, P. J. Org. Chem. 1989, 54, 4298-4301. 1H NMR (CDCl3) δ 7.20 (t, J=8 Hz, 1 H), 6.79-6.70 (m, 3 H), 3.80 (s, 3 H), 2.75-2.68 (m, 2 H), 2.61 (t, J=8 Hz, 2 H), 1.82-1.45 (m, 6 H).

후처리

  1. customthe temperature below 45° C
  2. temperaturecooled to room temperature
  3. customthe layers separated
  4. extractionthe aqueous portion back-extracted with diethyl ether (2×300 mL)
  5. washThe combined organic extracts were washed with water (3×500 mL), 6N HCl (500 mL), brine (500 mL)
  6. dry with materialdried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo to a clear liquid
  9. distillationKugelrohr distillation (0.1 torr, 120° C.)

출처 및 근거

ORD 기록
ord-8783f740582a4ca89b031818f7cc24b6
출처 데이터셋
uspto-grants-1997_08
특허 번호
US05661185

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