Sodium Methoxide → HCID 54374993, compound

HRID 653337Notes

Reaction equation

HRID 653337 reaction equation
[C:1]([NH:4][C@@H:5]1[C@@H:20]([O:21]C(=O)C)[C@H:19]([O:25][C@@H:26]2[O:63][C@H:62]([CH2:64][O:65]C(=O)C)[C@H:37]([O:38][C@H:39]3[O:56][C@H:55]([CH2:57][O:58]C(=O)C)[C@H:50]([O:51]C(=O)C)[C@H:45]([O:46]C(=O)C)[C@H:40]3[O:41]C(=O)C)[C@H:32]([O:33]C(=O)C)[C@H:27]2[O:28]C(=O)C)[C@@H:18]([CH2:69][O:70]C(=O)C)[O:17][C@H:6]1[O:7][CH2:8][CH2:9][S:10][CH2:11][CH2:12][C:13]([O:15][CH3:16])=[O:14])(=[O:3])[CH3:2].C[O-].[Na+]>CO>[C:1]([NH:4][C@@H:5]1[C@@H:20]([OH:21])[C@H:19]([O:25][C@@H:26]2[O:63][C@H:62]([CH2:64][OH:65])[C@H:37]([O:38][C@H:39]3[O:56][C@H:55]([CH2:57][OH:58])[C@H:50]([OH:51])[C@H:45]([OH:46])[C@H:40]3[OH:41])[C@H:32]([OH:33])[C@H:27]2[OH:28])[C@@H:18]([CH2:69][OH:70])[O:17][C@H:6]1[O:7][CH2:8][CH2:9][S:10][CH2:11][CH2:12][C:13]([O:15][CH3:16])=[O:14])(=[O:3])[CH3:2]

Participants

4

Reactant 2

HCID 10942334Sodium MethoxideHCID 86741644HCID 86741644, compound

Product 1

HCID 54374993HCID 54374993, compoundYield 75.7%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

Compound 81 (350 mg, 0.3 mmol) was dissolved in methanol (10 ml) by warming and then rapidly cooled. Methanolic sodium methoxide (0.2M, 0.2 ml) was added and the mixture was stirred at room temperature for 18 h, neutralized (Duolite C-26 (H+) resin), filtered and concentrated. The residue was dissolved in methanol (7 ml) and methanolic hydrazine hydrate (0.1M, 3 ml) was added. The mixture was refluxed for 33 h while two additional portions (2×3 ml) were added (after 24 and 30 h). The reaction was monitored by TLC (SiO2,chloroform methanol:water 65:35:10, lower phase). The solvent was removed and the residue was treated with a mixture of acetic anhydride (2.5 ml), ethanol (12 ml), and water (4 ml) at room temperature for 1 h. The ethanol was removed and the residue was partitioned between water (20 ml) and dichloromethane (5 ml). The aqueous phase was washed with dichloromethane (3×5 ml) and concentrated. The residue was chromatographed {Sephadex G-10 column. 3×57 cm, water) to give 82 (157 mg, 75%) with [α]D22 +34° (c 0.7, water). 1H-NMR [(CD3)2SO+D2O, 50°, Me4Si]δ inter alia 4.80 (d, 1H, J=3.5 Hz, H1"), 4.40 (d, 1H, J=8 Hz, H1 or H1'), 4.28 (d, 1H, J=7 Hz, H1or H1'), 4.08 (dt, 1H, J=6 and 1 Hz), 3.61 (s, CH3O), 2.75-2.70 and 2.61-2.54 (m, each 2H, SCH2CH2CO), 2.64 (t, 2H, J=7 Hz, OCH2CH2S), 1.80 (s, 3H, MeCON). 13C-NMR (D2O, TSP) δ 178.0, 177.3, 106.1, 103.8, 103.1, 81.6, 80.1, 78.2, 77.7, 75.3, 75.0, 73.7, 73.6, 72.1 (CH2), 72.0, 71.8, 71.4, 63.3 (CH2), 63.2 (CH2), 62.9 (CH2), 58.0 (C2), 55.2 (CH3O), 37.1 (CH 2), 33.8 (CH2), 29.4 (CH2), 23.2.

Workup

  1. temperatureby warming
  2. temperaturerapidly cooled
  3. filtrationneutralized (Duolite C-26 (H+) resin), filtered
  4. concentrationconcentrated
  5. dissolutionThe residue was dissolved in methanol (7 ml)
  6. additionmethanolic hydrazine hydrate (0.1M, 3 ml) was added
  7. temperatureThe mixture was refluxed for 33 h while two additional portions (2×3 ml)
  8. additionwere added (after 24 and 30 h)
  9. customThe solvent was removed
  10. additionthe residue was treated with a mixture of acetic anhydride (2.5 ml), ethanol (12 ml), and water (4 ml) at room temperature for 1 h
  11. customThe ethanol was removed
  12. customthe residue was partitioned between water (20 ml) and dichloromethane (5 ml)
  13. washThe aqueous phase was washed with dichloromethane (3×5 ml)
  14. concentrationconcentrated
  15. customThe residue was chromatographed {Sephadex G-10 column

Sources & evidence

ORD record
ord-5767cbadb373400d8a643ccf5fa8a086
Source dataset
uspto-grants-1987_06
Patent number
US04675392

Reaction notes

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