1-Propanol → HCID 15280850, compound

HRID 1734654Notes

Reaction equation

HRID 1734654 reaction equation
C([O:4][C@@H:5]1[C@H: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][C@H:7]([CH2:22][O:23]C(=O)C)[C@@H:6]1[O:27]C(=O)C)(=O)C.[CH2:31](O)[CH2:32]C>[Ni]>[Cl:18][C:14]1[C:15]([Cl:17])=[CH:16][C:11]2[N:10]([C@H:9]3[C@@H:5]([OH:4])[C@@H:6]([OH:27])[C@@H:7]([CH2:22][OH:23])[CH2:8]3)[C:31]([CH3:32])=[N:19][C:12]=2[CH:13]=1

Participants

4

Reactant 2

HCID 10311-PropanolHCID 15280843HCID 15280843, compound

Product 1

HCID 15280850HCID 15280850, compoundYield 26%

Reagents, catalysts & solvents 1

HCID 935NickelCatalyst

Procedure

(1R, 2S, 3R, 5R)-3-(Acetoxymethyl)-5-(4,5-dichloro-2-nitroanilino)-1,2-cyclopentanediyl diacetate (1.29 g, 2.78 mmol) in n-propanol (100 mL) was shaken with Raney nickel (Aldrich, slurry in water, 200 mg wet) under hydrogen (40 psi) on a Parr shaker for 4 hours. Catalyst was filtered off with Celite and the volatiles were evaporated in vacuo. The residual oil was refluxed in 96% formic acid (45 mL) for 5 hours. Concentrated hydrochloric acid (5 mL) was added and reflux continued for an additional 4 hours. Volatiles were evaporated in vacuo and the residue was dissolved in 1N sodium hydroxide (10 mL). The solution was stirred at ambient temperature for 18 hours, neutralized with acetic acid, and concentrated in vacuo. The residue was chromatographed on silica gel. Elution with 15% methanol-chloroform gave (1R, 2S, 3R, 5R)-5-(5,6-dichloro-2-methyl-1H-benzimidazol-1-yl)-3-(hydroxymethyl)-1,2-cyclopentanediol as white powder (236 mg, 26%), m.p. 198°-200° C.; 1H-NMR(DMSO-d6)δ: 8.30 and 7.72 (both s, 1 each, 2 aromatic CH), 5.0-4.8 (m, 3, 2 OH and NCH), 4.56 (t, J=5.1 Hz, 1, CH2OH), 4.2-4.1 (m, 2, 2 OCH), 3.8-3.5 (m, 2, CH2O), 2.58 (s, 3, CH3), 2.4-2.2 (m, 1, CH), 2.2-1.9 (m, 2, CH2); mass spectrum(CI): 331(M+1); [α]20589 -13.5°, [α]20578 -13.9°, [α]20546 -15.9°, [α]20436 -30.3° (c=0.251, methanol).

Workup

  1. filtrationCatalyst was filtered off with Celite
  2. customthe volatiles were evaporated in vacuo
  3. temperatureThe residual oil was refluxed in 96% formic acid (45 mL) for 5 hours
  4. additionConcentrated hydrochloric acid (5 mL) was added
  5. temperaturereflux
  6. customVolatiles were evaporated in vacuo
  7. dissolutionthe residue was dissolved in 1N sodium hydroxide (10 mL)
  8. concentrationconcentrated in vacuo
  9. customThe residue was chromatographed on silica gel
  10. washElution with 15% methanol-chloroform

Sources & evidence

ORD record
ord-848da49becf145baa4f6d9911a5438d2
Source dataset
uspto-grants-1996_07
Patent number
US05534535

Reaction notes

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