3-Nitrobenzyl alcohol → 4-Methoxybenzyl (6R,7R)-3-(5-acetoxymethyl-tetrahydrofuran-2-yl)-7-phenylacetamidoceph-3-em-4-carboxylate

HRID 376611

Reaktionsgleichung

Reaktionsgleichung von HRID 376611
[PH5].[C:2]([O:5][CH2:6][C@@H:7]1[O:11][C@H:10]([C:12]2[CH2:13][S:14][C@@H:15]3[C@H:31]([NH:32][C:33](=[O:41])[CH2:34][C:35]4[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=4)[C:30](=[O:42])[N:16]3[C:17]=2[C:18]([O:20][CH2:21][C:22]2[CH:27]=[CH:26][C:25]([O:28][CH3:29])=[CH:24][CH:23]=2)=[O:19])[CH2:9][CH2:8]1)(=[O:4])[CH3:3].[N+](C1C=C(C=CC=1)CO)([O-])=O.C([O-])(=O)C.[Na+].C(OC[C@H]1O[C@@H](C2CS[C@@H]3[C@H](NC(=O)CC4C=CC=CC=4)C(=O)N3C=2C(OCC2C=CC(OC)=CC=2)=O)CC1)(=O)C>C1(C)C=CC=CC=1.C(Cl)(Cl)Cl.C(OCC)(=O)C.CCCCCC>[C:2]([O:5][CH2:6][CH:7]1[O:11][CH:10]([C:12]2[CH2:13][S:14][C@@H:15]3[C@H:31]([NH:32][C:33](=[O:41])[CH2:34][C:35]4[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=4)[C:30](=[O:42])[N:16]3[C:17]=2[C:18]([O:20][CH2:21][C:22]2[CH:27]=[CH:26][C:25]([O:28][CH3:29])=[CH:24][CH:23]=2)=[O:19])[CH2:9][CH2:8]1)(=[O:4])[CH3:3]

Komponenten

9

Edukt 5

HCID 692673-Nitrobenzyl alcohol2×HCID 517045Sodium Acetate2×HCID 569933374-methoxybenzyl (6R,7R)-3-[(2S,5R)-5-acetoxymethyltetrahydrofuran-2-yl]-7-phenylacetamidoceph-3-em-4-carboxylateHCID 1317216384-methoxybenzyl (6R,7R)-3-[(2R,5S)-5-acetoxymethyltetrahydrofuran-2-yl]-7-phenylacetamidoceph-3-em-4-carboxylateHCID 178527699HCID 178527699, Verbindung

Produkt 1

HCID 542139684-Methoxybenzyl (6R,7R)-3-(5-acetoxymethyl-tetrahydrofuran-2-yl)-7-phenylacetamidoceph-3-em-4-carboxylate

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 1140TolueneLösungsmittelHCID 6212ChloroformLösungsmittel2×HCID 21226206Ethyl acetate hexaneLösungsmittel

Versuchsvorschrift

A solution of the phosphorane from Example 31(g) (517mg) in dry toluene (100ml) was heated at reflux under dry argon for 8 hours and evaporated. the residue was chromatographed on silica gel eluting with ethyl acetate/hexane mixtures to give two fractions. The less polar fraction contained 4-methoxybenzyl (6R,7R)-3-[(2S,5R)-5-acetoxymethyltetrahydrofuran-2-yl]-7-phenylacetamidoceph-3-em-4-carboxylate, a foam (105mg); vmax (CHCl3) 3410, 1784, 1726 and 1683cm-1 ; δH (CDCl3) 1.53-1.83 (3H, m), 2.09 (3H, s), 2.19-2.36 (1H, m), 3.30 and 3.55 (2H, ABq, J 18.9Hz), 3.60 and 3.69 (2H, ABq, J 16.2Hz), 3.81 (3H, s), 4.01-4.21 (3H, m), 4.90 (1H, d, J 4.8Hz), 4.96 (1H, dd, J 8.3, 6.7Hz), 5.12 and 5.17 (2H, AA'q, J 12.5Hz), 5.81 (1H, dd, J 9.2, 4.8Hz), 5.97 (1H, d, J 9.2Hz), 6.85-6.92 (2H, m), 7.25-7.41 (7H, m). [Mass spectrum: +ve ion (3-nitrobenzyl alcohol, sodium acetate) MH+ (581), MNa+ (603)]. The more polar fraction contained 4-methoxybenzyl (6R,7R)-3-[(2R,5S)-5-acetoxymethyltetrahydrofuran-2-yl]-7-phenylacetamidoceph-3-em-4-carboxylate, a solid (191mg), m.p. 185-187° C. (needles ex ethyl acetate/hexane); vmax (CHCl3) 3407, 1785, 1731 and 1682cm-1 ; δH (CDCl3) 1.53-1.78 (2H, m), 1.90-2.05 (2H, m), 2.08 (3H, s), 3.35 and 3.57 (2H, ABq, J 18.0Hz), 3.61 and 3.69 (2H, ABq, J 16.2Hz), 3.80 (3H, s), 4.01-4.19 (3H, m), 4.91 (1H, d, J 4.8Hz), 5.12-5.27 (3H, m), 5.74 (1H, dd, J 4.8, 9.0Hz), 6.04 (1H, d, J 9.0Hz), 6.85-6.91 (2H, m), 7.25-7.41 (7H, m). [Mass spectrum: +ve ion (3-nitrobenzyl alcohol, sodium acetate) MH+ (581), MNa+ (603)].

Aufarbeitung

  1. temperatureat reflux under dry argon for 8 hours
  2. customevaporated
  3. customthe residue was chromatographed on silica gel eluting with ethyl acetate/hexane
  4. customto give two fractions

Quellen und Nachweise

ORD-Eintrag
ord-343f20869b5d4e42bb5488726ab0e83e
Quelldatensatz
uspto-grants-2000_02
Patentnummer
US06020329

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