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

HRID 2050673노트

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HRID 2050673 반응식
[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

참가 물질

7

반응물 4

HCID 10563Barium CarbonateHCID 24408Bromine2회HCID 24477Sodium ThiosulfateHCID 1317168873-O-benzyl-N-benzyloxycarbonyl-2,6-imino-2,5,6-trideoxy-D-lyxo-hexose

생성물 1

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

시약·촉매·용매 2

HCID 962Water용매HCID 312751,4-Dioxane용매

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온도
0 °C

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-4d9e375b0cc6485aa41ec3e02c5e9b08
출처 데이터셋
uspto-grants-1991_05
특허 번호
US05013842

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