Ethanol → HCID 86748564, compound

HRID 1609031Notes

Reaction equation

HRID 1609031 reaction equation
[Cl:1][C:2]1[C:15]([Cl:16])=[CH:14][C:5]([NH:6][C@@H:7]2[CH2:11][C@H:10]([CH2:12][OH:13])[CH:9]=[CH:8]2)=[C:4]([N+:17]([O-])=O)[CH:3]=1.O.[CH2:21](O)C>[Fe].O.O.O.O.O.O.O.S([O-])([O-])(=O)=O.[Fe+2]>[Cl:1][C:2]1[C:15]([Cl:16])=[CH:14][C:5]2[N:6]([C@@H:7]3[CH2:11][C@H:10]([CH2:12][OH:13])[CH:9]=[CH:8]3)[CH:21]=[N:17][C:4]=2[CH:3]=1

Participants

6

Reactant 3

HCID 702EthanolHCID 962WaterHCID 15280838HCID 15280838, compound

Product 1

HCID 86748564HCID 86748564, compoundYield 82%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 62662Ferrous sulfate heptahydrateCatalyst

Procedure

(±)-cis-[4-(4,5-Dichloro-2-nitroanilino)-2-cyclopenten-1-yl]methanol (5.00 g, 16.5 mmol) in ethanol (100 mL)-water (35 mL) was heated while iron powder (325 mesh, 99.9%, Aldrich, 9.2 g, 0.165 equiv) and iron(II) sulfate heptahydrate (Aldrich, 98+%, 2.3 g, 8.2 mequiv) were added. The mixture was refluxed 1.75 hours. Solids were filtered off and the ethanol filtrate-wash concentrated to an oil. Triethylorthoformate (75 mL) and methanesulfonic acid (0.05 mL) were added to the oil and the resulting solution stirred at ambient temperature for 18 hours. Concentration in vacuo left an oil which was redissolved in 1N hydrochloric acid (25 mL)-dioxane(5 mL). After 3 hours, the pH was adjusted to 7 with 1N sodium hydroxide and the solution extracted with chloroform (3×50 mL). The contents of the dried (sodium sulfate) chloroform solution was chromatographed on silica gel. Title compound was eluted with 5% methanol-chloroform and crystallized from ethyl acetate-hexanes to give white crystals (3.85 g, 82%), m.p. 166°-169° C.; 1H-NMR(DMSO-d6) and mass spectrum(CI) consistent with structure.

Workup

  1. additionwere added
  2. temperatureThe mixture was refluxed 1.75 hours
  3. filtrationSolids were filtered off
  4. washthe ethanol filtrate-wash
  5. concentrationconcentrated to an oil
  6. additionTriethylorthoformate (75 mL) and methanesulfonic acid (0.05 mL) were added to the oil
  7. concentrationConcentration in vacuo
  8. waitleft an oil which
  9. dissolutionwas redissolved in 1N hydrochloric acid (25 mL)-dioxane(5 mL)
  10. waitAfter 3 hours
  11. extractionthe solution extracted with chloroform (3×50 mL)
  12. dry with materialThe contents of the dried (sodium sulfate) chloroform solution
  13. customwas chromatographed on silica gel
  14. washTitle compound was eluted with 5% methanol-chloroform
  15. customcrystallized from ethyl acetate-hexanes

Sources & evidence

ORD record
ord-8c5c2c0111414f138c2b496803f4d5ef
Source dataset
uspto-grants-1995_03
Patent number
US05399580

Reaction notes

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