Ethyl Acetate → HCID 67084795, 화합물

HRID 475662

반응식

HRID 475662 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 2734143alpha-AcetobromogalactoseHCID 4192832Benzenethiosulfonic acid

생성물 1

HCID 67084795HCID 67084795, 화합물수율 67.4%

시약·촉매·용매 2

HCID 74236Tetrabutylammonium Bromide촉매HCID 6342Acetonitrile용매

반응 조건

온도
70 °C

실험 절차

2,3,4,6-Tetra-O-acetyl-α-galactopyranosyl bromide (2.0 g, 5 mmol) was dissolved in anhydrous acetonitrile (80 mL). To this sodium phenylthiosulfonate (2.02 g, 10.3 mmol) and tetrabutylammonium bromide (160 mg, 0.5 mmol) were added. The resulting mixture was stirred under argon at 70° C. After a 5 h period, t.l.c. (petrol:ethyl acetate, 1:1) indicated the formation of a product (Rf 0.4) with complete consumption of the starting material (Rf 0.6). The solution was concentrated in vacuo. The crude oil was partitioned between DCM (50 mL) and water (50 mL), and the aqueous layer re-extracted with DCM (2×50 mL). The combined organics were washed with brine (100 mL), dried (MgSO4), filtered and concentrated in vacuo. The residue was purified by flash column chromatography (petrol:ethyl acetate, 2:1) to afford the title product (1.7 g, 65%, 2 steps) as a white crystalline solid; mp 53-54° C.; [α]D27+24.2 (c, 1.0 in CHCl3); δH (400 MHz, CDCl3) 1.98, 2.03, 2.06, 2.11 (4×3H, 4×s, 4×OAc), 3.85 (1H, dd, J5,6 8.8 Hz, J6,6′ 14.0 Hz, H-6), 3.95-4.00 (2H, m, H-5, H-6), 5.11 (1H, dd, J2,3 9.7 Hz, J3,4 3.3 Hz, H-3), 5.23 (1H, at, J10.3 Hz, H-2), 5.25 (1H, d, J1,2 10.2 Hz, H-1), 5.43 (1H, dd, J3,4 3.6 Hz, J4,5 1.0 Hz, H-4), 7.54-7.68 (3H, m, Ar—H), 7.93-7.97 (2H, m, Ar—H).

후처리

  1. customwith complete consumption of the starting material (Rf 0.6)
  2. concentrationThe solution was concentrated in vacuo
  3. customThe crude oil was partitioned between DCM (50 mL) and water (50 mL)
  4. extractionthe aqueous layer re-extracted with DCM (2×50 mL)
  5. washThe combined organics were washed with brine (100 mL)
  6. dry with materialdried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customThe residue was purified by flash column chromatography (petrol:ethyl acetate, 2:1)

출처 및 근거

ORD 기록
ord-9be9341264ba4ff2af741b983e7ecb7b
출처 데이터셋
uspto-grants-2014_01
특허 번호
US08637578B2

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