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 653343노트

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HRID 653343 반응식
[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]

참가 물질

6

반응물 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

생성물 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

시약·촉매·용매 1

HCID 6344Dichloromethane용매

실험 절차

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.

후처리

  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)

출처 및 근거

ORD 기록
ord-08c76fe2d94b4898a20eea2049bcf985
출처 데이터셋
uspto-grants-1987_06
특허 번호
US04675392

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