Ammonia methanol → HCID 54044812, compound

HRID 1734641Notes

Reaction equation

HRID 1734641 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].N.[CH3:32]O>>[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:32]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

3

Reactant 2

HCID 21705897Ammonia methanolHCID 54275101HCID 54275101, compound

Product 1

HCID 54044812HCID 54044812, compound

Procedure

(±)(1R*, 2S*, 3R*, 5R*)-3-(Acetoxymethyl)-5-(4,5-dichloro-2-nitroanilino)-1,2-cyclopentanediyl diacetate (5.00 g, 10.8 mmol) was stirred in ammonia/methanol (ca. 2N, 100 mL) at ambient temperature for 18 hours. Evaporation of volatiles in vacuo left residual orange solid (±)-(1R*, 2S*, 3R*, 5R*)-5-(4,5-dichloro-2-nitroanilino)-3-(hydroxymethyl)-1,2-cyclopentanediol having an identical Rf on silica gel TLC plates to that of the chiral sample described in Example 54. This solid was reduced with Raney nickel/hydrogen(45 psi) in isopropanol (200 mL). Catalyst was filtered off with Celite. The filtrate-wash was evaporated to dryness in vacuo. The residue was refluxed in formic acid (96%, 50 mL) for one hour, as described in Example 2. The oil remaining on evaporation of the formic acid was dissolved in methanol. The pH was adjusted to 13 with aqueous 5N sodium hydroxide and the solution was stirred at ambient temperature for one hour to hydrolyze formate esters. The pH was adjusted to 7 with 1N hydrochloric acid and volatiles removed by evaporation in vacuo. Pyridine (100 mL) and acetic anhydride (4 mL) were added to the residue and the mixture stirred at ambient temperature overnight. Evaporation of volatiles in vacuo followed by chromatography on silica gel with 1% methanol-chloroform gave (±)(1R*, 2S*, 3R*, 5R*)-3-(acetoxymethyl)-5-(5,6-dichloro-1H-benzimidazol-1-yl)-1,2-cyclopentanediyl diacetate as white crystals from ethanol-water (2.6 g, 53%), 1H-NMR(DMSO-d6) consistent with structure.

Workup

  1. customEvaporation of volatiles in vacuo
  2. waitleft residual orange solid (±)-(1R*, 2S*, 3R*, 5R*)-5-(4,5-dichloro-2-nitroanilino)-3-(hydroxymethyl)-1,2-cyclopentanediol having an identical Rf on silica gel TLC plates to that of the chiral sample
  3. filtrationCatalyst was filtered off with Celite
  4. customThe filtrate-wash was evaporated to dryness in vacuo
  5. temperatureThe residue was refluxed in formic acid (96%, 50 mL) for one hour
  6. customThe oil remaining on evaporation of the formic acid
  7. dissolutionwas dissolved in methanol
  8. customremoved by evaporation in vacuo
  9. additionPyridine (100 mL) and acetic anhydride (4 mL) were added to the residue
  10. stirringthe mixture stirred at ambient temperature overnight
  11. customEvaporation of volatiles in vacuo

Sources & evidence

ORD record
ord-4fcff0c2316b4ce4906563b188a698c6
Source dataset
uspto-grants-1996_07
Patent number
US05534535

Reaction notes

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