Hydrochloric Acid → tert-butyl 4-(tert-butylcarbamoyl)-4-(N-methylacetamido)oct-7-enylcarbamate

HRID 579540ノート

反応式

HRID 579540 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].[CH3:22][NH3+:23].[C:24]([N+:28]#[C-])([CH3:27])([CH3:26])[CH3:25].Cl.FC(F)(F)[CH2:33][OH:34]>C(OCC)(=O)C>[C:24]([NH:28][C:33]([C:2]([N:23]([CH3:22])[C:18](=[O:21])[CH3:19])([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:34])([CH3:25])([CH3:26])[CH3:27]

参加物

7

反応物 5

HCID 313Hydrochloric AcidHCID 64092,2,2-TrifluoroethanolHCID 23577Tert-Butyl isocyanideHCID 11564973Tert-butyl 4-oxooct-7-enylcarbamateHCID 14420923Methylammoniumacetat

生成物 1

HCID 86663727tert-butyl 4-(tert-butylcarbamoyl)-4-(N-methylacetamido)oct-7-enylcarbamate収率 26%

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 (300 mg; 1.24 mmol), methylammonium acetate (680 mg, 7.46 mmol) in 2,2,2-trifluoroethanol (2 mL) was treated with tert-butyl isocyanide (0.56 mL, 5.0 mmol) and stirred at room temperature for 5 days. Ethyl acetate (5 mL) and 2 M aq HCl (2 mL) were added and the solution was vigorously stirred for 3 additional 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 oil residue was purified by flash column chromatography (2% methanol in dichloromethane) to give tert-butyl 4-(tert-butylcarbamoyl)-4-(N-methylacetamido)oct-7-enylcarbamate (130 mg, 26%). 1H NMR (CDCl3, 500 MHz) δ 5.81-5.73 (m, 1H), 5.40 (s, 1H), 5.05-4.96 (m, 2H), 4.62 (bs, 1H), 3.15-3.09 (m, 2H), 3.01 (s, 3H) 2.17-2.12 (m, 2H), 2.10 (s, 3H) 2.04-1.94 (m, 2H), 1.77-1.71 (m, 2H), 1.43 (s, 9H), 1.38-1.34 (m, 2H), 1.32 (s, 9H). ESI MS found for C21H39N3O4 m/z [420.5 (M+Na+), 442.4 (M+HCOO−), 396.6 (M−1)].

後処理

  1. stirringthe solution was vigorously stirred for 3 additional 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 oil residue was purified by flash column chromatography (2% methanol in dichloromethane)

出典と根拠

ORDレコード
ord-a0e5572f1c124714b9d674d90a094608
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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