Water → 4-fluoro-1-(2,3,4,6-tetra-O-acetyl-beta-D-glucopyranosyl)indole-3-carboxaldehyde

HRID 544885Notes

Reaction equation

HRID 544885 reaction equation
[F:1][C:2]1[CH:10]=[CH:9][CH:8]=[C:7]2[C:3]=1[CH:4]=[CH:5][N:6]2[C@@H:11]1[O:28][C@H:27]([CH2:29][O:30][C:31](=[O:33])[CH3:32])[C@@H:22]([O:23][C:24](=[O:26])[CH3:25])[C@H:17]([O:18][C:19](=[O:21])[CH3:20])[C@H:12]1[O:13][C:14](=[O:16])[CH3:15].CN(C)[CH:36]=[O:37].O(Cl)Cl.[P+3].O>ClCCCl>[F:1][C:2]1[CH:10]=[CH:9][CH:8]=[C:7]2[C:3]=1[C:4]([CH:36]=[O:37])=[CH:5][N:6]2[C@@H:11]1[O:28][C@H:27]([CH2:29][O:30][C:31](=[O:33])[CH3:32])[C@@H:22]([O:23][C:24](=[O:26])[CH3:25])[C@H:17]([O:18][C:19](=[O:21])[CH3:20])[C@H:12]1[O:13][C:14](=[O:16])[CH3:15]

Participants

6

Reactant 4

HCID 962WaterHCID 6228DimethylformamideHCID 670204134-Fluoro-1-(2,3,4,6-tetra-O-acetyl-beta-D-glucopyranosyl)indoleHCID 178479710HCID 178479710, compound

Product 1

HCID 715002594-fluoro-1-(2,3,4,6-tetra-O-acetyl-beta-D-glucopyranosyl)indole-3-carboxaldehyde

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Conditions

Temperature
70 °C

Procedure

4-Fluoro-1-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-indole (3.50 g) obtained in Example 2-(3) and N,N-dimethyl-formamide (3.49 ml) were dissolved in 1,2-dichloroethane (70 ml), and thereto was added dropwise phosphorus(III) oxychloride (2.10 ml). The mixture was stirred at 70° C. for 1 hour, and thereto was added water (100 ml) at 0° C. The resultant mixture was extracted with ethyl acetate (200 ml) twice, and the combined organic layer was washed with brine (40 ml) and dried over magnesium sulfate. The insoluble materials were filtered off, and the filtrate was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (hexane:ethyl acetate=90:10-50:50) followed by recrystallization from ethyl alcohol (20 ml) to give 4-fluoro-1-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)indole-3-carboxaldehyde (2.93 g) as colorless crystals. mp 190-192° C. APCI-Mass m/Z 511 (M+NH4) 1H-NMR (DMSO-d6) δ 1.64 (s, 3H), 1.98 (s, 3H), 2.00 (s, 3H), 2.05 (s, 3H), 4.12 (A part of ABX, J=12.4, 2.5 Hz, 1H), 4.17 (B part of ABX, J=12.4, 5.5 Hz, 1H), 4.33 (ddd, J=10.0, 5.5 and 2.5 Hz, 1H), 5.32 (t, J=9.8 Hz, 1H), 5.56 (t, J=9.6 Hz, 1H), 5.66 (t, J=9.3 Hz, 1H), 6.36 (d, J=9.0 Hz, 1H), 7.11 (dd, J=10.6, 8.0 Hz, 1H), 7.38 (td, J=8.1, 5.1 Hz, 1H), 7.65 (d, J=8.3 Hz, 1H), 8.53 (s, 1H), 10.0 (d, J=2.9 Hz, 1H).

Workup

  1. extractionThe resultant mixture was extracted with ethyl acetate (200 ml) twice
  2. washthe combined organic layer was washed with brine (40 ml)
  3. dry with materialdried over magnesium sulfate
  4. filtrationThe insoluble materials were filtered off
  5. customthe filtrate was evaporated under reduced pressure
  6. customThe residue was purified by silica gel column chromatography (hexane:ethyl acetate=90:10-50:50)
  7. customfollowed by recrystallization from ethyl alcohol (20 ml)

Sources & evidence

ORD record
ord-a5112d4584954faabd7c9137751a45cc
Source dataset
uspto-grants-2011_05
Patent number
US07935674B2

Reaction notes

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