Methanol → {2-[(2,2-Dimethyl-[1,3]dioxolan-4-ylmethyl)-amino]-propyl}-carbamic acid tert-butyl ester

HRID 219495

反応式

HRID 219495 の反応式
[C:1]([O:5][C:6]([NH:8][CH2:9][CH2:10][CH2:11]OS(C)(=O)=O)=[O:7])([CH3:4])([CH3:3])[CH3:2].[CH3:17][C:18]1([CH3:25])[O:22][CH:21]([CH2:23][NH2:24])[CH2:20][O:19]1.CO>C(OCC)(=O)C>[C:1]([O:5][C:6](=[O:7])[NH:8][CH2:9][CH:10]([NH:24][CH2:23][CH:21]1[CH2:20][O:19][C:18]([CH3:25])([CH3:17])[O:22]1)[CH3:11])([CH3:2])([CH3:3])[CH3:4]

参加物

5

反応物 3

HCID 887MethanolHCID 41223491,3-Dioxolane-4-methanamine, 2,2-dimethyl-HCID 114141093-((Tert-butoxycarbonyl)amino)propyl methanesulfonate

生成物 1

HCID 68496101{2-[(2,2-Dimethyl-[1,3]dioxolan-4-ylmethyl)-amino]-propyl}-carbamic acid tert-butyl ester収率 32.6%

試薬・触媒・溶媒 1

HCID 8857Ethyl Acetate溶媒

実験手順

The commercially available Tert-butyl-N-(2-hydroxypropyl)carbamate (10 g, 57.0 mmol)) and trietylamine (12 ml, 85.6 mmol) were dissolved in dichloromethane (60 mL) and cooled to 0° C. Methanesulfonyl chloride (4.9 ml, 62.7 mmol) was added dropwise to the ice-cold solution and the reaction was allowed to warm up to room temperature with stirring overnight. The reaction was then quenched with NaOH (1M, 5 ml). The organics were washed with water (2×100 ml) and then brine, collected, dried over MgSO4, filtered and evaporated under reduced pressure to give methanesulfonic acid 3-tert-butoxycarbonylamino-propyl ester (13.5 g). The crude methanesulfonic acid 3-tert-butoxycarbonylamino-propyl ester (13.5 g, 53 mmol) and 2,2-dimethyl-1,3-dioxolane-4-methanamine (12 g, 91.6 mmol) were stirred overnight at room temperature. The mixture was dissolved in ethyl acetate (100 ml) and washed with water (3×100 ml) and brine. The organics were collected, dried over MgSO4, filtered and evaporated under reduced pressure to give an oil. This was purified by silica column chromatography eluting with ethyl acetate: methanol to give the desired product {2-[(2,2-Dimethyl-[1,3]dioxolan-4-ylmethyl)-amino]-propyl}-carbamic acid tert-butyl ester (4.74 g, 17.3 mmol). Mass Spec (ESI) m/z: [M+H]+=289.12. 1H NMR (CDCl3; 300 MHz) δ=5.15 (s, br, 1H), 4.19 (quin, 1H), 4.02 (t, 1H), 3.66 (t, 1H), 3.18 (q, 2H), 2.70 (m, 4H), 1.63 (quin, 2H), 1.42 (s, 9H), 1.40 (s, 3H), 1.40 (s, 3H). 13C NMR (CDCl3; 300 MHz) δ=156.00, 109.05, 78.85, 75.23, 67.47, 52.30, 47.91, 39.20, 29.69, 28.35, 26.81, 25.37.

後処理

  1. washwashed with water (3×100 ml) and brine
  2. customThe organics were collected
  3. dry with materialdried over MgSO4
  4. filtrationfiltered
  5. customevaporated under reduced pressure
  6. customto give an oil
  7. customThis was purified by silica column chromatography
  8. washeluting with ethyl acetate

出典と根拠

ORDレコード
ord-f5cea4b29d134f4a81a667882383030d
出典データセット
uspto-grants-2012_06
特許番号
US08202511B2

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