HCID 131728429, compound → HCID 68770077, compound

HRID 1172353Notes

Reaction equation

HRID 1172353 reaction equation
[N+:1]([C@@H:4]1[CH2:9][C:8]([C:10]([O:12][CH2:13]C)=[O:11])=[CH:7][CH2:6][C@H:5]1[C:15]1[CH:20]=[C:19]([F:21])[C:18]([F:22])=[CH:17][C:16]=1[F:23])([O-])=O>C(O)C.Cl.[Fe]>[NH2:1][C@@H:4]1[CH2:9][C:8]([C:10]([O:12][CH3:13])=[O:11])=[CH:7][CH2:6][C@H:5]1[C:15]1[CH:20]=[C:19]([F:21])[C:18]([F:22])=[CH:17][C:16]=1[F:23]

Participants

5

Reactant 1

HCID 131728429HCID 131728429, compound

Product 1

HCID 68770077HCID 68770077, compoundYield 75.8%

Reagents, catalysts & solvents 3

HCID 23925IronCatalyst3×HCID 313Hydrochloric AcidSolventHCID 702EthanolSolvent

Conditions

Temperature
45 °C

Procedure

A mixture of trans-ethyl 5-nitro-4-(2,4,5-trifluorophenyl)cyclohex-1-enecarboxylate (500 g, 1.59 mol) and Fe powder (90 g, 1.6 mol) in ethanol (3.2 L) and 2 M HCl (3.2 L) was heated to 45° C., whereupon the internal temperature of the reaction increased to 65° C. over the course of 0.5 hours. After the internal temperature had fallen to 45° C., a second portion of Fe powder (135 g, 2.4 mol) was added, resulting in an increase in internal temperature to 73° C. After thirty minutes, a third aliquot of Fe powder (90 g, 1.6 mol) was added, and the reaction was allowed to stir for one hour, after which the heating bath was removed. Ammonium hydroxide (˜100 mL) was then added to the ambient mixture until the pH was 8. The mixture was filtered though celite, eluting with boiling EtOH. The ethanol was removed under reduced pressure, and the aqueous was acidified with concentrated HCl to pH ˜3. The aqueous layer was then washed with diethyl ether (3×1 L), and the combined dark organic layers were discarded. The aqueous layer was basified with ammonium hydroxide, and the resulting emulsion was filtered through celite (eluting with hot EtOH). The filtrate was concentrated under reduced pressure, and the residue was partitioned between ethyl acetate and saturated aqueous NaHCO3. The layers were separated, and the organic was washed with saturated aqueous NaHCO3, dried over Na2SO4, filtered, and concentrated under reduced pressure to give the title compound as an oil (344 g, 75%).

Workup

  1. temperatureincreased to 65° C. over the course of 0.5 hours
  2. customhad fallen to 45° C.
  3. customresulting in
  4. temperaturean increase in internal temperature to 73° C
  5. waitAfter thirty minutes
  6. customafter which the heating bath was removed
  7. additionAmmonium hydroxide (˜100 mL) was then added to the ambient mixture until the pH was 8
  8. filtrationThe mixture was filtered though celite
  9. washeluting with boiling EtOH
  10. customThe ethanol was removed under reduced pressure
  11. washThe aqueous layer was then washed with diethyl ether (3×1 L)
  12. filtrationthe resulting emulsion was filtered through celite (eluting with hot EtOH)
  13. concentrationThe filtrate was concentrated under reduced pressure
  14. customthe residue was partitioned between ethyl acetate and saturated aqueous NaHCO3
  15. customThe layers were separated
  16. washthe organic was washed with saturated aqueous NaHCO3
  17. dry with materialdried over Na2SO4
  18. filtrationfiltered
  19. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-e3ea4397f9ce43d291e53319850a9024
Source dataset
uspto-grants-2010_11
Patent number
US07834012B2

Reaction notes

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