Ethyl Acetate → 2,3,4,6-Tetra-O-acetyl-beta-D-glucopyranosyl phenylthiosulfonate

HRID 475661

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HRID 475661 반응식
[C:1]([O:4][C@@H:5]1[C@@H:10]([O:11][C:12](=[O:14])[CH3:13])[C@H:9]([O:15][C:16](=[O:18])[CH3:17])[C@@H:8]([CH2:19][O:20][C:21](=[O:23])[CH3:22])[O:7][C@@H:6]1Br)(=[O:3])[CH3:2].[C:25]1([S:31]([O-:34])(=[O:33])=[S:32])[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1.[Na+].C(OCC)(=O)C>C(#N)C.[Br-].C([N+](CCCC)(CCCC)CCCC)CCC>[C:25]1([S:31]([O:34][C@@H:6]2[O:7][C@H:8]([CH2:19][O:20][C:21](=[O:23])[CH3:22])[C@@H:9]([O:15][C:16](=[O:18])[CH3:17])[C@H:10]([O:11][C:12](=[O:14])[CH3:13])[C@H:5]2[O:4][C:1](=[O:3])[CH3:2])(=[O:33])=[S:32])[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1

참가 물질

6

반응물 3

HCID 8857Ethyl AcetateHCID 101776alpha-D-Glucopyranosyl bromide, tetraacetateHCID 4192832Benzenethiosulfonic acid

생성물 1

HCID 114434942,3,4,6-Tetra-O-acetyl-beta-D-glucopyranosyl phenylthiosulfonate수율 89.2%

시약·촉매·용매 2

HCID 74236Tetrabutylammonium Bromide촉매HCID 6342Acetonitrile용매

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온도
70 °C

실험 절차

2,3,4,6-Tetra-O-acetyl-α-D-glucopyranosyl bromide (207 mg, 0.5 mmol) was dissolved in anhydrous acetonitrile (5 mL). To this sodium phenylthiosulfonate (201 mg, 1 mmol) and tetrabutylammonium bromide (16 mg, 0.05 mmol) were added. The resulting mixture was stirred under argon at 70° C. After a 4.5 h period, thin layer chromatography (t.l.c.) (petrol:ethyl acetate, 1:1) indicated the formation of a product (Rf 0.5) with complete consumption of the starting material (Rf 0.3). The solution was concentrated in vacuo. The crude solid was partitioned between dichloromethane (DCM, 20 mL) and water (20 mL), and the aqueous layer re-extracted with DCM (2×20 mL). The combined organics were washed with brine (20 mL), dried over MgSO4, filtered and concentrated in vacuo. The residue was purified by flash column chromatography (petrol:ethyl acetate, 1:1) to afford the title product (225 mg, 88%) as a white crystalline solid; mp 129-130° C.; [α]D25+51.2 (c, 1.0 in CHCl3); νmax (KBr) 1754 (s, C═O), 1376 (s, C═C) cm−1; δH; (400 MHz, C6D6) 1.68, 1.72, 1.73, 1.75 (4×3H, 4×s, 4×OAc), 3.09 (1H, ddd, J4,5 10.2 Hz, J5,6 2.4 Hz, J5,6′ 4.2 Hz, H-5), 3.83 (1H, dd, J5,6 2.4 Hz, J6,6′ 12.7 Hz, H-6),4.08 (1H, dd, J5,6′ 4.2 Hz, J6,6′ 12.6 Hz, H-6′), 5.17-5.23 (2H, m, H-2, H -4), 5.40 (1H, d, J1,2 10.2 Hz, H-1), 5.44 (1H, at, J9.4 Hz, H-3), 6.98-7.03 (3H, m, Ar—H), 7.90-7.92 (2H, m, Ar—H). The structure of the product was further confirmed by single crystal X-ray diffraction.

후처리

  1. customthe formation of a product (Rf 0.5) with complete consumption of the starting material (Rf 0.3)
  2. concentrationThe solution was concentrated in vacuo
  3. customThe crude solid was partitioned between dichloromethane (DCM, 20 mL) and water (20 mL)
  4. extractionthe aqueous layer re-extracted with DCM (2×20 mL)
  5. washThe combined organics were washed with brine (20 mL)
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customThe residue was purified by flash column chromatography (petrol:ethyl acetate, 1:1)

출처 및 근거

ORD 기록
ord-db71093ff5b14821a6a432d619198428
출처 데이터셋
uspto-grants-2014_01
특허 번호
US08637578B2

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