Isopropanol → HCID 54044812, compound

HRID 1734628Notes

Reaction equation

HRID 1734628 reaction equation
[C:1]([O:4][CH:5]1[CH:9]([NH:10][C:11]2[CH:16]=[C:15]([Cl:17])[C:14]([Cl:18])=[CH:13][C:12]=2[N+:19]([O-])=O)[CH2:8][CH:7]([CH2:22][O:23][C:24](=[O:26])[CH3:25])[CH:6]1[O:27][C:28](=[O:30])[CH3:29])(=[O:3])[CH3:2].[CH:31](O)(C)C>[Ni]>[C:1]([O:4][CH:5]1[CH:9]([N:10]2[C:11]3[CH:16]=[C:15]([Cl:17])[C:14]([Cl:18])=[CH:13][C:12]=3[N:19]=[CH:31]2)[CH2:8][CH:7]([CH2:22][O:23][C:24](=[O:26])[CH3:25])[CH:6]1[O:27][C:28](=[O:30])[CH3:29])(=[O:3])[CH3:2]

Participants

4

Reactant 2

HCID 3776IsopropanolHCID 54275101HCID 54275101, compound

Product 1

HCID 54044812HCID 54044812, compound

Reagents, catalysts & solvents 1

HCID 935NickelCatalyst

Procedure

(±)-(1R*, 2S*, 3S*, 5S*)-3-(Acetoxymethyl)-5-(4,5-dichloro-2-nitroanilino)-1,2-cyclopentanediyl diacetate (2.75 g, 5.93 mmol) and Raney nickel (aqueous slurry, Aldrich, 300 mg wet) in isopropanol (250 mL) was shaken under hydrogen (40 psi) in a Parr shaker for 2.25 hours. Catalyst was filtered off with Celite and the filtrate acidified with 98% formic acid (5 mL) and concentrated to an orange oil. The oil was diluted with additional 98% formic acid (45 mL) and the resulting orange solution refluxed for 40 minutes. Volatiles were removed and the remaining dark oil dissolved in chloroform (100 mL). The chloroform solution was washed with saturated aqueous sodium bicarbonate (3×10 mL), dried (sodium sulfate), and evaporated to a foam which was chromatographed on silica gel. Title compound eluted with methanol:chloroform/3:97 as a white foam from ethyl acetate (2.26 g, 86%); 1H-NMR (DMSO-d6)δ: 8.57, 8.17, 7.97 (all s, 1 each, 3 benzimidazole CH), 5.6 (m, 1, CHO), 5.3-5.1 (m, 2, CHO and CHN), 4.35-4.15 (m, 2, CH2O), 2.6-2.4 (m overlapping solvent, 2 CH), 2.10, 2.06, 1.92 (all s) overlapped by 2.0 (m, total 10, 3CH3CO and CH).

Workup

  1. filtrationCatalyst was filtered off with Celite
  2. concentrationconcentrated to an orange oil
  3. additionThe oil was diluted with additional 98% formic acid (45 mL)
  4. temperaturethe resulting orange solution refluxed for 40 minutes
  5. customVolatiles were removed
  6. dissolutionthe remaining dark oil dissolved in chloroform (100 mL)
  7. washThe chloroform solution was washed with saturated aqueous sodium bicarbonate (3×10 mL)
  8. dry with materialdried (sodium sulfate)
  9. customevaporated to a foam which
  10. customwas chromatographed on silica gel
  11. washTitle compound eluted with methanol

Sources & evidence

ORD record
ord-bb08220cb0414d309fdd137a29413ca6
Source dataset
uspto-grants-1996_07
Patent number
US05534535

Reaction notes

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