Formaldehyde → 2-(p-Aminophenylthio)ethyl 4-O-(beta-D-galactopyranosyl)-beta-D-galactopyranoside

HRID 653327Notes

Reaction equation

HRID 653327 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([SH:8])=[CH:4][CH:3]=1.[H-].[Na+].C([O:14][C@@H:15]1[C@@H:24]([O:25]C(=O)C)[C@@H:23]([O:29][C@@H:30]2[O:47][C@H:46]([CH2:48][O:49]C(=O)C)[C@H:41]([O:42]C(=O)C)[C@H:36]([O:37]C(=O)C)[C@H:31]2[O:32]C(=O)C)[C@@H:22]([CH2:53][O:54]C(=O)C)[O:21][C@H:16]1[O:17][CH2:18][CH2:19]Br)(=O)C.C[O-].[Na+].CO.C=O>CN(C)C=O.O.C(OCC)(=O)C.C(CC(C)(C)C)(C)C>[C@@H:30]1([O:29][C@H:23]2[C@@H:22]([CH2:53][OH:54])[O:21][C@@H:16]([O:17][CH2:18][CH2:19][S:8][C:5]3[CH:6]=[CH:7][C:2]([NH2:1])=[CH:3][CH:4]=3)[C@H:15]([OH:14])[C@H:24]2[OH:25])[O:47][C@H:46]([CH2:48][OH:49])[C@H:41]([OH:42])[C@H:36]([OH:37])[C@H:31]1[OH:32]

Participants

9

Reactant 5

HCID 712FormaldehydeHCID 145104-AminothiophenolHCID 24758Sodium hydrideHCID 205840672-Bromoethyl 2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-beta-D-galactopyranosyl)-beta-D-galactopyranosideHCID 23694274Sodium methanolate methanol

Product 1

HCID 542866292-(p-Aminophenylthio)ethyl 4-O-(beta-D-galactopyranosyl)-beta-D-galactopyranoside

Reagents, catalysts & solvents 3

HCID 962WaterSolvent2×HCID 6228DimethylformamideSolvent2×HCID 18516502EtOAc isooctaneSolvent

Procedure

p-Aminothiophenol (205 mg; 1.64 mmol) was dissolved in dimethylformamide (4 ml). Sodium hydride (70 mg; 2.9 mmol) was added and the mixture was stirred under nitrogen for 20 min at room temperature. 2-Bromoethyl 2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-β-D-galactopyranoside 14 (640 mg; 0.86 mmol) in dimethylformamide (7 ml) was added and the reaction mixture was stirred under nitrogen for 2 h (TLC:SiO2, ethyl acetate:isooctane 3:1) and poured into cold water (40 ml). The water solution was extracted with ether (4×20 ml) and the combined ether solutions were washed with water (10 ml) and dried (sodium sulfate). Evaporation gave a residue that contained a series of partly de-acetylated compounds. Evaporation of the water solution gave an additional amount of partly de-acetylated material. The combined residues were de-acetylated (sodium methoxide/methanol) and the product (after evaporation) was filtered through a column (SiO2, ethyl acetate/methanol 2:3) which gave crystalline (needles) 26. Yield: 425 mg (99%). Recrystallization from methanol gave an analytical sample: mp 104°-106°, [α]D 23 -0.8° (c 1.1; H2O); 1H-NMR (DMSO-D6 plus D2O, 50° C., TMS) δ 7.13, 6.58 (d, 2H each, J=8.5 Hz, aromatic H), 4.28 (d, 1H, J=7.0 Hz, H1'), 4.28 (d, 1H, J=7.5 Hz, H1), 2.90 (t, 2H, J=7.0 Hz, CH2 --S) ppm. 13C-NMR (DMSO-D6 plus D2O) δ 149.2, 136.6, 124.7, 119.7 (aromatic C), 107.0, 105.5 (Cl, Cl'), 79.7, 77.8, 76.9, 75.9, 75.5, 74.2, 73.9, 71.4, 70.7, (C2-C5, C2'-C5', CH2O), 63.8, 63.1 (C6, C6'), 37.6 (CH2 --S) ppm.

Workup

  1. extractionThe water solution was extracted with ether (4×20 ml)
  2. washthe combined ether solutions were washed with water (10 ml)
  3. dry with materialdried (sodium sulfate)
  4. customEvaporation
  5. customgave a residue that
  6. customEvaporation of the water solution
  7. customgave an additional amount of partly de-acetylated material
  8. customthe product (after evaporation)
  9. filtrationwas filtered through a column (SiO2, ethyl acetate/methanol 2:3) which
  10. customgave crystalline (needles) 26
  11. customRecrystallization from methanol
  12. customgave an analytical sample

Sources & evidence

ORD record
ord-e47cafcb543542959dc5cdbbfe75de1e
Source dataset
uspto-grants-1987_06
Patent number
US04675392

Reaction notes

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