Sodium Dithionite → HCID 178501111, compound

HRID 538055Notes

Reaction equation

HRID 538055 reaction equation
[CH3:1][O:2][C:3]([C@H:5]1[CH2:10][CH2:9][C@H:8]([CH2:11][NH:12][C:13]2[CH:18]=[C:17]([C:19]([F:22])([F:21])[F:20])[CH:16]=[CH:15][C:14]=2[N+:23]([O-])=O)[CH2:7][CH2:6]1)=[O:4].[O-]S(S([O-])=O)=O.[Na+].[Na+].[O:34]1CCOC[CH2:35]1>[OH-].[NH4+]>[CH3:1][O:2][C:3]([C@H:5]1[CH2:10][CH2:9][C@H:8]([CH2:11][N:12]2[C:13]3[CH:18]=[C:17]([C:19]([F:22])([F:21])[F:20])[CH:16]=[CH:15][C:14]=3[NH:23][C:35]2=[O:34])[CH2:7][CH2:6]1)=[O:4]

Participants

5

Reactant 3

HCID 24489Sodium DithioniteHCID 312751,4-DioxaneHCID 178501112HCID 178501112, compound

Product 1

HCID 178501111HCID 178501111, compoundYield 49%

Reagents, catalysts & solvents 1

HCID 14923Ammonium HydroxideSolvent

Conditions

Temperature
50 °C

Procedure

trans 4-[(2-Nitro-5-trifluoromethyl-phenylamino)-methyl]-cyclohexane carboxylic acid methyl ester (1.8 g, 5.0 mmol) was dissolved in 35 ml of a mixture 4:1 of dioxane and 25% ammonium hydroxide. Na2S2O4 (2.6 g, 15.0 mmol) was added and the mixture was stirred at 50° C. for 4 hours. The solvent was evaporated and the crude dissolved in 20 ml MeOH. 4 ml of concentrated (37%) HCl and 10 ml of water were added and the mixture was stirred at 50° C. for three hours and then at room temperature overnight. The MeOH was evaporated under reduced pressure and 20 ml of DCM and 5 ml of a saturated solution of Na2CO3 were added. The organic phase was separated and the solvent removed. The crude material was dissolved in THF (40 ml) and 1,1-carbonyldiimidazole (1.62 g, 10 mmol) was added. The mixture was stirred at room temperature overnight. The solvent was evaporated and the crude dissolved in DCM (20 ml). The organic solution was washed with 10 ml of 1M HCl and the solvent removed under reduced pressure. The titled compound was purified by silica column using ethyl acetate cyclohexane 1:1 as eluent. 0.87 g (yield 49%) of the titled compound were isolated.

Workup

  1. customThe solvent was evaporated
  2. dissolutionthe crude dissolved in 20 ml MeOH
  3. concentration4 ml of concentrated (37%) HCl and 10 ml of water
  4. additionwere added
  5. stirringthe mixture was stirred at 50° C. for three hours
  6. customat room temperature
  7. customovernight
  8. customThe MeOH was evaporated under reduced pressure and 20 ml of DCM and 5 ml of a saturated solution of Na2CO3
  9. additionwere added
  10. customThe organic phase was separated
  11. customthe solvent removed
  12. dissolutionThe crude material was dissolved in THF (40 ml)
  13. stirringThe mixture was stirred at room temperature overnight
  14. customThe solvent was evaporated
  15. dissolutionthe crude dissolved in DCM (20 ml)
  16. washThe organic solution was washed with 10 ml of 1M HCl
  17. customthe solvent removed under reduced pressure
  18. customThe titled compound was purified by silica column

Sources & evidence

ORD record
ord-327342a01d624dd9983ca488f91b1360
Source dataset
uspto-grants-2014_10
Patent number
US08865704B2

Reaction notes

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