HCID 15511970, compound → HCID 15667489, compound

HRID 1604472Notes

Reaction equation

HRID 1604472 reaction equation
[C:1]([O:9][CH2:10][C@@H:11]1[C@@H:18]2[C@@H:14]([O:15][C:16](=[O:19])[CH2:17]2)[CH:13](SC2C=CC=CC=2)[O:12]1)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1>[Ni].C(O)C>[C:1]([O:9][CH2:10][C@@H:11]1[C@@H:18]2[C@@H:14]([O:15][C:16](=[O:19])[CH2:17]2)[CH2:13][O:12]1)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

4

Reactant 1

HCID 15511970HCID 15511970, compound

Product 1

HCID 15667489HCID 15667489, compoundYield 36.4%

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 702EthanolSolvent

Procedure

A 3-neck, 1000 mL round-bottom flask, equipped for overhead mechanical stirring, was charged with 29.6 g of 8 (80 mmol), 500 mL of ethanol and approximately 30 g of Raney-Ni (Aldrich, which had been washed to neutrality with distilled water). The resulting slurry was heated at reflux for 5 h while stirring vigorously. The reaction mixture was then cooled to room temperature, and the solids were carefully filtered off through a pad of celite. The residue was washed thoroughly with ethanol, and the combined filtrates were concentrated to afford a yellow solid which was purified by chromatography on silica gel to afford 7.63 g (36% yield) of 9 as a white solid. A small sample was recrystallized from acetone/hexane to afford colorless needles: mp 89.5-90.0° C.; [α]D22 +3.18 (c=0.8 in CHCl3); Rf 0.36 (60% EtOAc/hexane); 1H-NMR (CDCl3) δ 8.01 (m, 2H), 7.40-7.65 (m, 3H), 5.15 (m, 1H), 4.41 (m, 2H), 4.05-4.32 (m, 3H), 2.80-3.05 (m, 2H), 2.56 (d, 1H, J=15.7 Hz); MS m/z at 263 for (M+H)+.

Workup

  1. customA 3-neck, 1000 mL round-bottom flask, equipped for overhead mechanical stirring
  2. temperatureThe resulting slurry was heated
  3. temperatureat reflux for 5 h
  4. filtrationthe solids were carefully filtered off through a pad of celite
  5. washThe residue was washed thoroughly with ethanol
  6. concentrationthe combined filtrates were concentrated
  7. customto afford a yellow solid which
  8. customwas purified by chromatography on silica gel

Sources & evidence

ORD record
ord-a0017dddf48f4f71b8a5dadf1d5d3eb4
Source dataset
uspto-grants-1999_11
Patent number
US05994397

Reaction notes

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