Hydrazine hydrate (1:1) → Ethyl 2-acetamido-2-deoxy-3,6-di-O-acetyl-4-O-[2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-alpha-D-galactopyranosyl)-beta-D-galactopyranosyl]-beta-glucopyranoside

HRID 653339Notes

Reaction equation

HRID 653339 reaction equation
[C:1]([O:4][C@H:5]1[C@H:14]([O:15][C@@H:16]2[O:53][C@H:52]([CH2:54][O:55][C:56](=[O:58])[CH3:57])[C@H:27]([O:28][C@H:29]3[O:46][C@H:45]([CH2:47][O:48][C:49](=[O:51])[CH3:50])[C@H:40]([O:41][C:42](=[O:44])[CH3:43])[C@H:35]([O:36][C:37](=[O:39])[CH3:38])[C@H:30]3[O:31][C:32](=[O:34])[CH3:33])[C@H:22]([O:23][C:24](=[O:26])[CH3:25])[C@H:17]2[O:18][C:19](=[O:21])[CH3:20])[C@@H:13]([CH2:59][O:60][C:61](=[O:63])[CH3:62])[O:12][C@@H:7]([O:8][CH2:9][CH2:10]Br)[C@@H:6]1[N:64]1C(=O)C2=CC=CC=[C:66]2[C:65]1=[O:74])(=[O:3])[CH3:2].O.NN>C[O-].[Na+].ClCCl.[Pd]>[C:65]([NH:64][C@@H:6]1[C@@H:5]([O:4][C:1](=[O:3])[CH3:2])[C@H:14]([O:15][C@@H:16]2[O:53][C@H:52]([CH2:54][O:55][C:56](=[O:58])[CH3:57])[C@H:27]([O:28][C@H:29]3[O:46][C@H:45]([CH2:47][O:48][C:49](=[O:51])[CH3:50])[C@H:40]([O:41][C:42](=[O:44])[CH3:43])[C@H:35]([O:36][C:37](=[O:39])[CH3:38])[C@H:30]3[O:31][C:32](=[O:34])[CH3:33])[C@H:22]([O:23][C:24](=[O:26])[CH3:25])[C@H:17]2[O:18][C:19](=[O:21])[CH3:20])[C@@H:13]([CH2:59][O:60][C:61](=[O:63])[CH3:62])[O:12][C@H:7]1[O:8][CH2:9][CH3:10])(=[O:74])[CH3:66]

Participants

6

Reactant 2

HCID 24654Hydrazine hydrate (1:1)HCID 867416432-Bromoethyl 3,6-di-O-acetyl-2-deoxy-2-phthalimido-4-O-[2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-alpha-D-galactopyranosyl)-beta-D-galactopyranosyl]-beta-D-glucopyranoside

Product 1

HCID 88636952Ethyl 2-acetamido-2-deoxy-3,6-di-O-acetyl-4-O-[2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-alpha-D-galactopyranosyl)-beta-D-galactopyranosyl]-beta-glucopyranosideYield 28.6%

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 6344DichloromethaneSolventHCID 10942334Sodium MethoxideSolvent

Procedure

Compound 78 (0.65 g, 0.58 mmol) was hydrogenated (10% Pd/C, 0.31 g, 40 psi) in methanolic sodium methoxide (0.02M, 56 ml) at room temperature for 20 h, filtered and neutralized with Duolite C-26 (H+) resin. The mixture was filtered and concentrated and the residue was dissolved in methanol (20 ml) and hydrazine hydrate (1.7 g, 34 mmol), refluxed for 23 h and concentrated. The residue was acetylated (acetic anhydride:pyridine 1:1 50 ml) at room temperature for 18 h. Co-concentration with toluene gave a residue that was dissolved in dichloromethane (75 ml) and washed with water (50 ml). The water phase was extracted with dichloromethane (25 ml) and the combined organic extracts were washed with water (10 ml), dried (Na2SO4), and concentrated. The residue was chromatographed (SiO2 -column, 1.5×46 cm, ethyl acetate) to give crystalline 87 (158 mg, 28%) with mp 130°-133°, [α]D22 +41° (c 0.7, chloroform). 1H-NMR (CDCl3, Me4Si) δ 5.73 (d, 1H, J=9.5 Hz, NH), 5.58 (bd, 1H, J~3 Hz, H4"), 5.39 (dd, 1H, J=11 and 3 Hz, H3"), 5.19 (dd, 1H, J=11 and 3.5 Hz, H2"), 5.12 (dd, 1H, J=11 and 8 Hz, H2'), 5.10 (dd, 1H, J=9.5 and 8 Hz, H3), 5.00 (d, 1H, J=3.5 Hz, H1"), 4.76 (dd, 1H, J=11 and 2.5 Hz, H3'), 4.58-4.37 (5H, inter alia H1, H1'), 4.55 (d, 1H, J=8 Hz, H1 or H1'), 4.46 (d, 1H, J=7.5 Hz, H1 or H1'), 4.23-3.96 (6H), 3.95-3.73 (3H), 3.71-3.45 (2H), 2.14, 2.11, 2.106, 2.084, 2.079, 2.076, 2.06, 2.05, 1.99, 1.97, 1.19 (t, 3H, J=7 Hz, CH3CH2). 13C-NMR (CDCl3, Me4Si) δ 170.6 (2C), 170.51, 170.46 (2C), 170.4, 170.3, 170.1, 169.7, 169.1, 101.1 (d, J=164 Hz, C1 or C1'), 100.7 (d, J=160 Hz, C1 or C1'), 99.6 (d, J=174 Hz, C1"), 77.0, 76.1, 72.8, 72.7, 72.5, 71.9, 69.0, 68.7, 67.9, 67.1 (2C), 65.0 (CH2), 62.5 (CH2), 61.4 (CH2), 60.3 (CH2), 53.4 (C2), 23.2-20.5, 15.1 (CH3CH2).

Workup

  1. customat room temperature
  2. customfor 20 h
  3. filtrationfiltered
  4. filtrationThe mixture was filtered
  5. concentrationconcentrated
  6. dissolutionthe residue was dissolved in methanol (20 ml)
  7. concentrationconcentrated
  8. customat room temperature
  9. customfor 18 h
  10. concentrationCo-concentration with toluene
  11. customgave a residue that
  12. washwashed with water (50 ml)
  13. extractionThe water phase was extracted with dichloromethane (25 ml)
  14. washthe combined organic extracts were washed with water (10 ml)
  15. dry with materialdried (Na2SO4)
  16. concentrationconcentrated
  17. customThe residue was chromatographed (SiO2 -column, 1.5×46 cm, ethyl acetate)

Sources & evidence

ORD record
ord-5bcfaf5df94d4d6daf336c3cc11d69dc
Source dataset
uspto-grants-1987_06
Patent number
US04675392

Reaction notes

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