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Thiophenol → 2-(p-Nitrophenylthio)ethyl 2,3,4,6-tetra-O-acetyl-beta-D-galactopyranoside

HRID 653326
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Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 653326
[N+:1]([C:4]1[CH:9]=[CH:8][C:7]([SH:10])=[CH:6][CH:5]=1)([O-:3])=[O:2].[H-].[Na+].[C:13]([O:16][C@@H:17]1[C@@H:26]([O:27][C:28](=[O:30])[CH3:29])[C@@H:25]([O:31][C:32](=[O:34])[CH3:33])[C@@H:24]([CH2:35][O:36][C:37](=[O:39])[CH3:38])[O:23][C@H:18]1[O:19][CH2:20][CH2:21]Br)(=[O:15])[CH3:14].C1(S)C=CC=CC=1>CN(C)C=O.CCOCC.C(OCC)(=O)C.C(CC(C)(C)C)(C)C>[C:13]([O:16][C@@H:17]1[C@@H:26]([O:27][C:28](=[O:30])[CH3:29])[C@@H:25]([O:31][C:32](=[O:34])[CH3:33])[C@@H:24]([CH2:35][O:36][C:37](=[O:39])[CH3:38])[O:23][C@H:18]1[O:19][CH2:20][CH2:21][S:10][C:7]1[CH:8]=[CH:9][C:4]([N+:1]([O-:3])=[O:2])=[CH:5][CH:6]=1)(=[O:15])[CH3:14]
KomponentenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

8

Edukt 4

HCID 7969ThiophenolHCID 158094-NitrobenzenethiolHCID 24758Sodium hydrideHCID 105757262-bromoethyl 2,3,4,6-tetra-O-acetyl-beta-D-galactopyranoside

Produkt 1

HCID 545191362-(p-Nitrophenylthio)ethyl 2,3,4,6-tetra-O-acetyl-beta-D-galactopyranoside

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 3283Diethyl EtherLösungsmittel
HCID 6228DimethylformamideLösungsmittel2×
HCID 18516502EtOAc isooctaneLösungsmittel

Versuchsvorschrift

p-Nitrothiophenol (50 mg; 0.32 mmol) was added to a suspension of sodium hydride (oil-free; 11 mg; 0.46 mmol) in dimethylformamide (3 ml) at room temperature and with stirring. 2-Bromoethyl 2,3,4,6-tetra-O-acetyl-β-D-galactopyranoside (1) (110 mg; 0.24 mmol) in dimethylformamide (3 ml) was added during 10 min to the thiophenol solution and the reaction mixture was stirred for another 75 min (TLC: SiO2, ethyl acetate:isooctane 1:1). The reaction mixture was poured into ice-cold water (20 ml) and ether (40 ml). The aqueous phase was extracted further with ether (40 ml) and the combined organic phases were washed with cold water (20 ml) and dried (sodium sulfate). Evaporation and chromatography (SiO2, ethyl acetate:isooctane 1:1) gave the title compound (25) as a light yellow oil. Yield: 80 mg (62%). [α]D23 -15.2° (c 1.1; CDCl3); 1H-NMR (CDCl3, TMS) δ 8.14, 7.36 (ABq, 4H, JAB =9.2 Hz, aromatic H), 5.40 (dd, 1H, J4,5 =1.0 Hz, H4), 5.22 (dd, 1H, J2,3 =10.5 Hz, H2), 5.01 (dd, 1H, J3,4 =3.4 Hz, H3), 4.52 (d, 1H, J1,2 =7.8 Hz, H1), 3.25 (t, 2H, J=6.5 Hz, S--CH2), 2.17, 2.05, 2.04, 1.99 (s, 3H each, CH3CO) ppm. 13C-NMR (CDCl3, TMS) δ 170.4, 170.2, 170.1, l69.4 (CO), 146.6, 145.3, 126.5, 124.1 (aromatic C), 101.4 (Cl), 70.9, 70.8, 68.5, 66.9 (C2-C5), 67.9 (CH2 --O) 61.2 (C6), 31.8 (S--CH2), 20.8, 20.7, 20.6 (CH3CO) ppm.

Aufarbeitung

  1. extractionThe aqueous phase was extracted further with ether (40 ml)
  2. washthe combined organic phases were washed with cold water (20 ml)
  3. dry with materialdried (sodium sulfate)
  4. customEvaporation and chromatography (SiO2, ethyl acetate:isooctane 1:1)

Quellen und Nachweise

ORD-Eintrag
ord-a75a6a942fdb47e286f909a18d51a4b0
Quelldatensatz
uspto-grants-1987_06
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US04675392

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