Pyridine → N-(t-butyldimethylsilyl)-4-[3-(p-nitrobenzyloxycarbonyl)-2-oxopropyl]-azetidin-2-one

HRID 247497ノート

反応式

HRID 247497 の反応式
N1C=CC=CC=1.[Si:7]([N:14]1[CH:17]([CH2:18][CH:19]([OH:34])[CH2:20][C:21]([O:23][CH2:24][C:25]2[CH:30]=[CH:29][C:28]([N+:31]([O-:33])=[O:32])=[CH:27][CH:26]=2)=[O:22])[CH2:16][C:15]1=[O:35])([C:10]([CH3:13])([CH3:12])[CH3:11])([CH3:9])[CH3:8].CC(O)C>C(Cl)Cl.[O-2].[O-2].[O-2].[Cr+6]>[Si:7]([N:14]1[CH:17]([CH2:18][C:19](=[O:34])[CH2:20][C:21]([O:23][CH2:24][C:25]2[CH:26]=[CH:27][C:28]([N+:31]([O-:33])=[O:32])=[CH:29][CH:30]=2)=[O:22])[CH2:16][C:15]1=[O:35])([C:10]([CH3:13])([CH3:12])[CH3:11])([CH3:9])[CH3:8]

参加物

6

反応物 3

HCID 1049PyridineHCID 3776IsopropanolHCID 12848994N-(t-butyldimethylsilyl)-4-[3-(p-nitrobenzyloxycarbonyl)-2-hydroxypropyl]-azetidin-2-one

生成物 1

HCID 12804721N-(t-butyldimethylsilyl)-4-[3-(p-nitrobenzyloxycarbonyl)-2-oxopropyl]-azetidin-2-one収率 58.3%

試薬・触媒・溶媒 2

HCID 10219390chromium (VI) trioxide触媒HCID 6344Dichloromethane溶媒2 回

実験手順

Anhydrous chromium trioxide (16.88 g 169 mmol) is added to a solution of anhydrous pyridine (27.3 ml, 338 mmol) in anhydrous methylene chloride (470 ml). The resulting mixture is stirred at room temperature for 30 minutes and then treated with a solution of N-(t-butyldimethylsilyl)-4-[3-(p-nitrobenzyloxycarbonyl)-2-hydroxypropyl]-azetidin-2-one (8.92 g, 21.1 mmol) in methylene chloride (80 ml). The reaction mixture is stirred an additional 15 minutes at room temperature and then treated with 2-propanol (6.75 ml). The methylene chloride phase is decanted from the dark, tary residue and evaporated under vacuum. The residue from this operation is triturated with diethyl ether (350 ml) and filtered through a pad of magnesium sulfate which is washed with additional ether (150 ml). The ethereal filtrate is washed with water (200 ml), 5% aqueous sodium bicarbonate (200 ml) and brine, dried with magnesium sulfate, filtered, evaporated under vacuum, and stripped with toluene to afford the crude product (5.99 g) as an amber oil. Chromatigraphy on a silica gel column using 3:2 petroleum ether-ethyl acetate as eluting solvent yields N-(t-butyldimethylsilyl)-4-[3-(p-nitrobenzyloxycarbonyl)-2-oxopropyl]-azetidin-2-one (5.17 g, 58%) as a pale yellow, viscous oil which solidifies. Trituration with diethyl ether gives the product as small, white crystals: mp 65°-66.5°, IR (CH2CL2) 1732, 1522, and 1350 cm) NMR (CDCl3) 8 0.20 (s, 3, CH3), 0.23 (s, 3, CH3), 0.93 (s, 9, C(CH3)3), 2.58 (dd, 1, J=2.7 and 15.7, H3β), 2.72 (dd, 1, J=9.4 and 18.2, CH2COCH2CO2), 3.19 (dd, 1, J=4.0 and 18.2, CH2COCH2CO2), 3.35 (dd, 1, J=5.3 and 15.7, H3α), 3.55 (s, 2,COCH2CO2), 3.90 (m, 1, H4), 5.30 (s, 2, CH2Ar), 7.55 and 8.25 (two d15, 4, J-8.5, ArH); MS m/e 405 (M+ -15), 363 (M+ -57), 321 (363-42) and 136.

後処理

  1. stirringThe reaction mixture is stirred an additional 15 minutes at room temperature
  2. customThe methylene chloride phase is decanted from the dark, tary residue
  3. customevaporated under vacuum
  4. customThe residue from this operation is triturated with diethyl ether (350 ml)
  5. filtrationfiltered through a pad of magnesium sulfate which
  6. washis washed with additional ether (150 ml)
  7. washThe ethereal filtrate is washed with water (200 ml), 5% aqueous sodium bicarbonate (200 ml) and brine
  8. dry with materialdried with magnesium sulfate
  9. filtrationfiltered
  10. customevaporated under vacuum
  11. customto afford the crude product (5.99 g) as an amber oil
  12. washas eluting solvent

出典と根拠

ORDレコード
ord-85da05bda701498cb0614680f35610e3
出典データセット
uspto-grants-1987_11
特許番号
US04707547

反応ノート

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