Boron trifluoride etherate → 2-Bromoethyl 2,3,6-tri-O-acetyl-4-O-{2,3,6-tri-O-acetyl-4-O-[2,3,4-tri-O-acetyl-6-O-(2,3,4,6-tetra-O-acetyl-alpha-D-glucopyranosyl)-alpha-D-glucopyranosyl]-alpha-D-glucopyranosyl]-beta-D-glucopyranoside

HRID 653343Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 653343
[C:1]([O:4][C@@H:5]1[O:82][C@H:81]([CH2:83][O:84][C:85](=[O:87])[CH3:86])[C@@H:16]([O:17][C@@H:18]2[O:75][C@H:74]([CH2:76][O:77][C:78](=[O:80])[CH3:79])[C@@H:29]([O:30][C@H:31]3[O:48][C@H:47]([CH2:49][O:50][C@H:51]4[O:68][C@H:67]([CH2:69][O:70][C:71](=[O:73])[CH3:72])[C@@H:62]([O:63][C:64](=[O:66])[CH3:65])[C@H:57]([O:58][C:59](=[O:61])[CH3:60])[C@H:52]4[O:53][C:54](=[O:56])[CH3:55])[C@@H:42]([O:43][C:44](=[O:46])[CH3:45])[C@H:37]([O:38][C:39](=[O:41])[CH3:40])[C@H:32]3[O:33][C:34](=[O:36])[CH3:35])[C@H:24]([O:25][C:26](=[O:28])[CH3:27])[C@H:19]2[O:20][C:21](=[O:23])[CH3:22])[C@H:11]([O:12][C:13](=[O:15])[CH3:14])[C@H:6]1[O:7][C:8](=[O:10])[CH3:9])(=O)[CH3:2].[Br:88]CCO.B(F)(F)F.CCOCC.C(OCC)(=O)C.C(CC(C)(C)C)(C)C>ClCCl>[C:8]([O:7][C@@H:6]1[C@@H:11]([O:12][C:13](=[O:15])[CH3:14])[C@H:16]([O:17][C@H:18]2[O:75][C@H:74]([CH2:76][O:77][C:78](=[O:80])[CH3:79])[C@@H:29]([O:30][C@H:31]3[O:48][C@H:47]([CH2:49][O:50][C@H:51]4[O:68][C@H:67]([CH2:69][O:70][C:71](=[O:73])[CH3:72])[C@@H:62]([O:63][C:64](=[O:66])[CH3:65])[C@H:57]([O:58][C:59](=[O:61])[CH3:60])[C@H:52]4[O:53][C:54](=[O:56])[CH3:55])[C@@H:42]([O:43][C:44](=[O:46])[CH3:45])[C@H:37]([O:38][C:39](=[O:41])[CH3:40])[C@H:32]3[O:33][C:34](=[O:36])[CH3:35])[C@H:24]([O:25][C:26](=[O:28])[CH3:27])[C@H:19]2[O:20][C:21](=[O:23])[CH3:22])[C@@H:81]([CH2:83][O:84][C:85](=[O:87])[CH3:86])[O:82][C@H:5]1[O:4][CH2:1][CH2:2][Br:88])(=[O:10])[CH3:9]

Komponenten

6

Edukt 4

HCID 8000Boron trifluoride etherateHCID 108982-BromoethanolHCID 18516502EtOAc isooctaneHCID 886555281,2,3,6-tetra-O-acetyl-4-O-{2,3,6-tri-O-acetyl-4-O-[2,3,4-tri-O-acetyl-6-O-(2,3,4,6-tetra-O-acetyl-alpha-D-glucopyranosyl)-alpha-D-glucopyranosyl]-beta-D-glucopyranosyl}-beta-D-glucopyranose

Produkt 1

HCID 867416462-Bromoethyl 2,3,6-tri-O-acetyl-4-O-{2,3,6-tri-O-acetyl-4-O-[2,3,4-tri-O-acetyl-6-O-(2,3,4,6-tetra-O-acetyl-alpha-D-glucopyranosyl)-alpha-D-glucopyranosyl]-alpha-D-glucopyranosyl]-beta-D-glucopyranoside

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel

Versuchsvorschrift

Compound 92 (12.54 g, 9.85 mmol) and 2-bromoethanol (2.5 g, 1.4 ml, 20 mmol) were dissolved in dichloromethane (50 ml). Borontrifluoride etherate (7.1 g, 6.3 ml, 50 mmol) was added dropwise at room temperature and the mixture was stirred until the reaction was finished (48 h, TLC: SiO2, ethyl acetate:isooctane 3:1). The mixture was washed (water, saturated sodium hydrogen carbonate), dried (Na2SO4) and evaporated. The residue (12.3 g) was chromatographed (SiO2, ethyl acetate:isooctane 3:2) to give 93 (4.95 g, 63% based on transformed 92 and unreacted 92 (5.05 g). Compound 93 had [α]D25 +109° (c 1.3, chloroform). 1H-NMR (CDCl3, Me4Si) δ 5.35, 5.28, 5.18 (3d, each 1H, J=3.8, 2.8 and 3.6 Hz, H1', H1", H1"'), 4.60 (d, 1H, J=7.9 Hz, H1), 3.42-3.49 (m, 2H, CH2 -Br). 13C-NMR (CDCl3, TMS) δ 170.6-169.3 (CO), 100.4 (Cl), 95.9, 95.7, 95.3 (Cl', Cl", Cl"'), 77.3. 75.0, 73.7, 72.7, 72.2, 71.9, 71.8, 70.7, 70.4, 70.1, 69.9, 69.8, 69.7, 69.4, 69.3, 68.9, 68.5, 68.4, 67.4, 63.0, 61.8, 29.9, 21.1-20.6.

Aufarbeitung

  1. washThe mixture was washed (water, saturated sodium hydrogen carbonate)
  2. dry with materialdried (Na2SO4)
  3. customevaporated
  4. customThe residue (12.3 g) was chromatographed (SiO2, ethyl acetate:isooctane 3:2)

Quellen und Nachweise

ORD-Eintrag
ord-08c76fe2d94b4898a20eea2049bcf985
Quelldatensatz
uspto-grants-1987_06
Patentnummer
US04675392

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