Hydrochloric Acid → Tert-butyl 4-acetamido-4-(tert-butylcarbamoyl)oct-7-enylcarbamate

HRID 579551ノート

反応式

HRID 579551 の反応式
O=[C:2]([CH2:14][CH2:15][CH:16]=[CH2:17])[CH2:3][CH2:4][CH2:5][NH:6][C:7](=[O:13])[O:8][C:9]([CH3:12])([CH3:11])[CH3:10].[C:18]([O-:21])(=O)[CH3:19].[NH4+:22].[C:23]([N+:27]#[C-])([CH3:26])([CH3:25])[CH3:24].Cl.FC(F)(F)[CH2:32][OH:33]>C(OCC)(=O)C>[C:18]([NH:22][C:2]([C:32](=[O:33])[NH:27][C:23]([CH3:26])([CH3:25])[CH3:24])([CH2:14][CH2:15][CH:16]=[CH2:17])[CH2:3][CH2:4][CH2:5][NH:6][C:7](=[O:13])[O:8][C:9]([CH3:12])([CH3:11])[CH3:10])(=[O:21])[CH3:19]

参加物

7

反応物 5

HCID 313Hydrochloric AcidHCID 64092,2,2-TrifluoroethanolHCID 23577Tert-Butyl isocyanideHCID 517165Ammonium AcetateHCID 11564973Tert-butyl 4-oxooct-7-enylcarbamate

生成物 1

HCID 86663730Tert-butyl 4-acetamido-4-(tert-butylcarbamoyl)oct-7-enylcarbamate収率 66%

試薬・触媒・溶媒 1

HCID 8857Ethyl Acetate溶媒

実験手順

A solution of tert-butyl 4-oxooct-7-enylcarbamate (Example 159, 2.17 g, 8.99 mmol) and ammonium acetate (4.16 g, 53.9 mmol) in 2,2,2-trifluoroethanol (7 mL) was treated with tert-butyl isocyanide (4.1 mL, 35.9 mmol) and stirred at room temperature for 3 days. Ethyl acetate (15 mL) and 2 M aq HCl (10 mL) were added and the solution was vigorously stirred for an additional 3 hrs. The phases were separated and the organic phase was washed successively with water and sat'd aq sodium chloride, dried over MgSO4, filtered and concentrated. The crude viscous yellow residue was purified by flash column chromatography (5-50% ethyl acetate in hexanes) to give tert-butyl 4-acetamido-4-(tert-butylcarbamoyl)oct-7-enylcarbamate (2.27 g, 66%). 1H NMR (CDCl3, 500 MHz) δ 6.97 (s, 1H), 5.79-5.70 (m, 1H), 5.56 (s, 1H), 4.99-4.92 (m, 2H), 4.55 (bs, 1H), 3.08-3.06 (m, 2H), 2.78-2.67 (m, 2H), 2.03-1.93 (m, 1H), 1.99 (s, 3H), 1.84-1.76 (m, 1H), 1.42 (s, 9H), 1.38-1.34 (m, 2H), 1.36 (s, 9H), 1.29-1.24 (m, 2H), ESI MS found for C20H37N3O4 m/z [406.5 (M+Na+), 384.6 (M+1), 382.5 (M−1)].

後処理

  1. stirringthe solution was vigorously stirred for an additional 3 hrs
  2. customThe phases were separated
  3. washthe organic phase was washed successively with water
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe crude viscous yellow residue was purified by flash column chromatography (5-50% ethyl acetate in hexanes)

出典と根拠

ORDレコード
ord-1fbf6ad20ac04546bb1823e6ab1789da
出典データセット
uspto-grants-2015_05
特許番号
US09040703B2

反応ノート

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