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Cesium carbonate → 2-(2-Methoxycarbonylethylthio)ethyl 2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-alpha-D-galactopyranosyl)-beta-D-galactopyranoside

HRID 653323
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 653323
[C:1]([O:4][C@@H:5]1[C@@H:14]([O:15][C:16](=[O:18])[CH3:17])[C@@H:13]([O:19][C@H:20]2[O:37][C@H:36]([CH2:38][O:39][C:40](=[O:42])[CH3:41])[C@H:31]([O:32][C:33](=[O:35])[CH3:34])[C@H:26]([O:27][C:28](=[O:30])[CH3:29])[C@H:21]2[O:22][C:23](=[O:25])[CH3:24])[C@@H:12]([CH2:43][O:44][C:45](=[O:47])[CH3:46])[O:11][C@H:6]1[O:7][CH2:8][CH2:9]Br)(=[O:3])[CH3:2].[SH:48][CH2:49][CH2:50][C:51]([O:53][CH3:54])=[O:52].C(=O)([O-])[O-].[Cs+].[Cs+].C(OCC)(=O)C.C(CC(C)(C)C)(C)C>[Cl-].C[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC.C1C=CC=CC=1.O>[C:1]([O:4][C@@H:5]1[C@@H:14]([O:15][C:16](=[O:18])[CH3:17])[C@@H:13]([O:19][C@H:20]2[O:37][C@H:36]([CH2:38][O:39][C:40](=[O:42])[CH3:41])[C@H:31]([O:32][C:33](=[O:35])[CH3:34])[C@H:26]([O:27][C:28](=[O:30])[CH3:29])[C@H:21]2[O:22][C:23](=[O:25])[CH3:24])[C@@H:12]([CH2:43][O:44][C:45](=[O:47])[CH3:46])[O:11][C@H:6]1[O:7][CH2:8][CH2:9][S:48][CH2:49][CH2:50][C:51]([O:53][CH3:54])=[O:52])(=[O:3])[CH3:2]
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Komponenten

8

Edukt 4

HCID 10796Cesium carbonateHCID 18050Methyl 3-mercaptopropionate2×HCID 18516502EtOAc isooctaneHCID 228870902-Bromoethyl 2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-alpha-D-galactopyranosyl)-beta-D-galactopyranoside

Produkt 1

HCID 54172652
2-(2-Methoxycarbonylethylthio)ethyl 2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-alpha-D-galactopyranosyl)-beta-D-galactopyranoside

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 21218Trioctylmethylammonium chlorideKatalysatorHCID 241BenzeneLösungsmittelHCID 962WaterLösungsmittel

Versuchsvorschrift

2-Bromoethyl 2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl)-β-D-galactopyranoside (15) (251 mg; 0.338 mmol), methyl 3-mercaptopropionate (38 μl; 0.35 mmol) methyltrioctylammonium chloride (ca 10 mg) and cesium carbonate (114 mg; 0.35 mmol) were dissolved in benzene (0.5 ml) and water (0.5 ml). The reaction mixture was stirred (magnet) over night and analyzed by TLC (SiO2, ethyl acetate:isooctane 4:1; reaction 2/3 completed). Methyl 3-mercaptopropionate (ca 20 μl) was added and the reaction mixture was stirred for 24 h (TLC showed complete reaction). The phases were separated, the water phase was extracted twice with methylene chloride and the combined organic phases were dried (sodium sulfate) which gave a yellow to green solution. Evaporation gave a syrup which was chromatographed (SiO2, ethyl acetate:isooctane 2:1) to give the title compound (22) as a syrup. Yield: 211 mg (80%). [α]D23 +70.0° (c 0.6; CHCl3); 1H-NMR (CDCl3, TMS) δ 5.57 (d, 1H, J3',4' =3.0 Hz, H4'), 5.39 (dd, 1H, J2',3' =11.0 Hz. H2'), 5.19 (dd, 1H, H3'), 5.17 (dd, 1H, J2,3 =11 Hz, H2), 5.00 (d, 1H, J1',2' =4.0 Hz, H1'), 4.80 (dd, 1H, J3,4 =3.0 Hz, H3), 4.51 (d, 1H, J1,2 =8.0 Hz, H1), 3.70 (s, 3H, CH3 --O), 2.82, 2.75, 2.63 (t, 2H each, J=7 Hz, CH2 --S, CH2 --CO), 2.13, 2.11, 2.08, 2.08, 2.06, 2.04, 1.98 (s, 3H each, CH3CO) ppm. 13C-NMR (CDCl3, TMS) δ 172.3 (COOCH3), 170.7, 170.6, 170.5, 170.4, 170.1, 169.8, 169.2 (CH3CO), 101.1 (Cl), 99.4 (Cl'), 77.1, 72.7, 72.0, 68.6, 68.5, 67.9, 67.4, 67.1 (C2-C5, C2'-C5'), 69.5 (OCH2), 62.0, 60.5 (C6, C6'), 51.8 (COOCH3), 34.7, 31.4, 27.4 (CH2S, CH2 --CO), 21.0, 20.7 (CH3CO) ppm.

Aufarbeitung

  1. stirringthe reaction mixture was stirred for 24 h
  2. custom(TLC showed complete reaction)
  3. customThe phases were separated
  4. extractionthe water phase was extracted twice with methylene chloride
  5. dry with materialthe combined organic phases were dried (sodium sulfate) which
  6. customgave a yellow to green solution
  7. customEvaporation
  8. customgave a syrup which
  9. customwas chromatographed (SiO2, ethyl acetate:isooctane 2:1)

Quellen und Nachweise

ORD-Eintrag
ord-36df67bfbe55479ca97689c189ee47e3
Quelldatensatz
uspto-grants-1987_06
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US04675392

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