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 653343ノート

反応式

HRID 653343 の反応式
[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]

参加物

6

反応物 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

生成物 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

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

実験手順

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.

後処理

  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)

出典と根拠

ORDレコード
ord-08c76fe2d94b4898a20eea2049bcf985
出典データセット
uspto-grants-1987_06
特許番号
US04675392

反応ノート

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