Water → 7-(1-Hydroxy-1-p-nitrobenzyloxycarbonylmethyl)-8-oxo-7-azabicyclo[4,2,0]-oct-3-ene

HRID 1388289ノート

反応式

HRID 1388289 の反応式
O.[C:2]([O:6][CH2:7][C:8]1[CH:13]=[CH:12][C:11]([N+:14]([O-:16])=[O:15])=[CH:10][CH:9]=1)(=[O:5])[CH:3]=[O:4].O.[O:18]=[C:19]1[CH:26]2[CH:21]([CH2:22][CH:23]=[CH:24][CH2:25]2)[NH:20]1>C1C=CC=CC=1>[OH:4][CH:3]([N:20]1[C:19](=[O:18])[CH:26]2[CH:21]1[CH2:22][CH:23]=[CH:24][CH2:25]2)[C:2]([O:6][CH2:7][C:8]1[CH:13]=[CH:12][C:11]([N+:14]([O-:16])=[O:15])=[CH:10][CH:9]=1)=[O:5]

参加物

5

反応物 3

HCID 962WaterHCID 3002787-Azabicyclo[4.2.0]oct-3-en-8-oneHCID 21934455p-Nitrobenzyl glyoxylate hydrate

生成物 1

HCID 127969397-(1-Hydroxy-1-p-nitrobenzyloxycarbonylmethyl)-8-oxo-7-azabicyclo[4,2,0]-oct-3-ene

試薬・触媒・溶媒 1

HCID 241Benzene溶媒

実験手順

p-Nitrobenzyl glyoxylate hydrate (9.08 g) was refluxed in benzene (150 ml) with provision for the removal of water. After 1 hour 8-oxo-7-azabicyclo[4.2.0]oct-3-ene (1) (2.46 g) was added and refluxing continued for 3.5 hours. The cooled solution was washed with water (x 2), then brine. After back extraction of the first aqueous extract with ethyl acetate, the organic solutions were dried over magnesium sulphate, filtered combined, and evaporated. Chromatography on silica, eluting with ethyl acetate-petroleum ether mixtures gave two separate isomers of the alcohol (54) (43%). Less polar isomer I m.p. 153-5° (crystalline plates ex ethyl acetate/ether), νmax (CHCl3) 3400 (broad), 1760, 1745, 1520, 1350 cm-1. δ ppm (CDCl3) 1.90-2.83 (4H, m, 2-CH2), 3.23-3.55 (1H, m, β-lactam proton), 4.00-4.20 (1H, m, β-lactam proton), 4.27 (1H, d, J 8 Hz, exchangeable with D2O, OH), 5.33 (2H, s, CH2Ar)-obscuring 1H, CHOH; 5.67-5.88 (2H, m, CH=CH), 7.55 (2H, d, J 8.5 Hz, Ar), 8.23 (2H, d, J 8.5 Hz, Ar) (Found: C, 58.07; H, 5.15; N, 8.51%, C16H16N2O6 requires C, 57.83; H, 4.85; N, 8.43%). More polar isomer II m.p. 118°-120° (fine crystalline needles ex ethyl acetate/ether). νmax (CHCl3) 3400 (broad), 1760-1745, 1520, 1350 cm-1. δ ppm (CDCl3) 1.83-2.77 (4H, m, 2-CH2), 3.25-3.55 (1H, m, β-lactam proton), 4.02-4.37 (2H, m, β-lactam proton and CHOH, -OH exchangeable with D2O), 5.31-5.98 [5H, 5.35 (2H, s, CH2Ar), obscuring, 1H, which sharpens to s, at δ 5.40 on D2O exchange, CHOH, and 2H, m, CH=CH], 7.56 (2H, d, J 8 Hz, Ar), 8.23 (2H, d, J 8 Hz, Ar) (Found: C, 57.95; H, 4.95; N, 8.50%. C16H16N2O6 requires C, 57.83; H, 4.85; N, 8.43%).

後処理

  1. temperaturerefluxing
  2. washThe cooled solution was washed with water (x 2)
  3. extractionAfter back extraction of the first
  4. extractionaqueous extract with ethyl acetate
  5. dry with materialthe organic solutions were dried over magnesium sulphate
  6. filtrationfiltered
  7. customevaporated
  8. washChromatography on silica, eluting with ethyl acetate-petroleum ether mixtures
  9. customgave two
  10. customseparate isomers of the alcohol (54) (43%)

出典と根拠

ORDレコード
ord-cbadc79899a04148a6c3ff1027d783c6
出典データセット
uspto-grants-1984_02
特許番号
US04431587

反応ノート

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