Barium Carbonate → 3-O-benzyl-N-benzyloxycarbonyl-2,6-imino-2,5,6-trideoxy-D-lyxo-hexono-1,4-lactone

HRID 2050673ノート

反応式

HRID 2050673 の反応式
[CH2:1]([O:8][C@H:9]1[C@H:16]([OH:17])[CH2:15][CH2:14][N:13]([C:18]([O:20][CH2:21][C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)=[O:19])[C@@H:10]1[CH:11]=[O:12])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(=O)([O-])[O-].[Ba+2].BrBr.S([O-])([O-])(=O)=S.[Na+].[Na+]>O1CCOCC1.O>[CH2:1]([O:8][C@H:9]1[C@H:16]2[CH2:15][CH2:14][N:13]([C:18]([O:20][CH2:21][C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=3)=[O:19])[C@@H:10]1[C:11]([O:17]2)=[O:12])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

参加物

7

反応物 4

HCID 10563Barium CarbonateHCID 24408Bromine2 回HCID 24477Sodium ThiosulfateHCID 1317168873-O-benzyl-N-benzyloxycarbonyl-2,6-imino-2,5,6-trideoxy-D-lyxo-hexose

生成物 1

HCID 145234483-O-benzyl-N-benzyloxycarbonyl-2,6-imino-2,5,6-trideoxy-D-lyxo-hexono-1,4-lactone収率 84.6%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 312751,4-Dioxane溶媒

反応条件

温度
0 °C

実験手順

A solution of 1,5-imino-1,2,5-trideoxy-D-arabino-hexitol (24) (407 mg, 1.10 mmol) in a 1:3 mixture of water and 1,4-dioxan containing barium carbonate (653 mg, 3.31 mmol), was cooled to 0° C. and treated with bromine (70 μl, 221 mg, 1.37 mmol), then stirred at room temperature for 24 hours. Sodium thiosulphate solution (1M, aqueous) was added until the bromine was removed then the solution acidified with hydrochloric acid (2M, aq, 30 ml) and centrifuged. The supernatent was removed and extracted with ethyl acetate (4×20 ml). The combined organic phase was dried, filtered and evaporated. Purification by flash chromatography gave 3-O-benzyl-N-benzyloxycarbonyl-2,6-imino-2,5,6-trideoxy-D-lyxo-hexono-1,4-lactone (342 mg, 84%) as a clear oil, [α]20D -13.7° (c, 1.42 in chloroform); νmax (film) 3030, 2880, 1790 (lactone CO), 1700 (Z CO), 1425, 1260, 1170, 1060, and 700 cm-1 ; 1H NMR δ 1.80-1.93 (1H, m, H-5); 2.28-2.35 (1H, m, H-5'); 3.15-3.20 (1H, m, H-6); 3.93-4.07 (1H, m, H-6'); 4.15, 4.28 (1H, 2×dd, H-3); 4.39-4.61 (2H, m, H-2, H-4); 4.74-4.83 (2H, m, CH2Ph; 5.04-5.20 (3H, m, H-1, CH2 -Z), 7.17-7.35 (10H, m, 2×H-Ph). 13C NMR δ 26.25 (t, C-5); 35.27, 35.49 (2×t, C-6); 65.92, 66.17 (2×d, C-4); 67.38 (t, CH2 -Z); 71.45 (t, CH2Ph); 75.86 (d, C-3); 127.87, 127.98, 128.08, 128.57 (4×d, HC-Ph); 136.78, 137.73 (2×s, C-Ph); 155.15 (s, C=O-Z); 170.34 (s, C-1). m/z (CI NH3): 91 (100%), 324 (M-CO2 +H+, 60%), 385 (M+NH4+, 25%). (Found C, 68.56; H, 5.96; N, 3.51. C21H21NO5 requires C, 68.68; H, 5.76; N, 3.81).

後処理

  1. customwas removed
  2. customThe supernatent was removed
  3. extractionextracted with ethyl acetate (4×20 ml)
  4. customThe combined organic phase was dried
  5. filtrationfiltered
  6. customevaporated
  7. customPurification by flash chromatography

出典と根拠

ORDレコード
ord-4d9e375b0cc6485aa41ec3e02c5e9b08
出典データセット
uspto-grants-1991_05
特許番号
US05013842

反応ノート

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