Ammonium Chloride → HCID 90410534, compound

HRID 1403716Notes

Reaction equation

HRID 1403716 reaction equation
[CH3:1][S:2]([N:5]1[CH2:10][CH2:9][CH:8]([O:11][C:12]2[CH:17]=[CH:16][C:15]([N+:18]([O-])=O)=[CH:14][CH:13]=2)[CH2:7][CH2:6]1)(=[O:4])=[O:3].[Cl-].[NH4+]>O.CCO.[Fe]>[CH3:1][S:2]([N:5]1[CH2:6][CH2:7][CH:8]([O:11][C:12]2[CH:17]=[CH:16][C:15]([NH2:18])=[CH:14][CH:13]=2)[CH2:9][CH2:10]1)(=[O:4])=[O:3]

Participants

6

Reactant 2

HCID 25517Ammonium ChlorideHCID 22052648HCID 22052648, compound

Product 1

HCID 90410534HCID 90410534, compoundYield 70%

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 702EthanolSolventHCID 962WaterSolvent

Procedure

A mixture of 1-methanesulfonyl-4-(4-nitro-phenoxy)-piperidine (9.07 g, 30.2 mmol), iron powder (˜325 mesh, 5.05 g, 90.6 mmol), ammonium chloride solution (6.46 g, 120.8 mmol) in water (50 mL) and EtOH (IMS grade, 150 mL) was heated at reflux for 2 hours. The cooled mixture was filtered through Celite® washing with DCM and the organic solvent removed under vacuum. The remaining aqueous was diluted with water and extracted into DCM (3×). The combined extracts were dried over Na2SO4 and concentrated under vacuum. Purification by silica gel column chromatography (0-10% EtOAc in DCM) followed by trituration from Et2O afforded the title compound (5.71 g, 70%) as an off white solid. 1H NMR (300 MHz, DMSO) δ 6.70 (d, J=8.5 Hz, 2H), 6.50 (d, J=8.5 Hz, 2H), 4.65 (br s, 2H), 4.22 (m, 1H), 3.32 (m, 2H), 3.07 (m, 2H), 2.88 (s, 3H), 1.90 (m, 2H), 1.67 (m, 2H). LCMS (m/z, Method A) ES+ 271.0 [M+1]+.

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 2 hours
  3. filtrationThe cooled mixture was filtered through Celite®
  4. washwashing with DCM
  5. customthe organic solvent removed under vacuum
  6. additionThe remaining aqueous was diluted with water
  7. extractionextracted into DCM (3×)
  8. dry with materialThe combined extracts were dried over Na2SO4
  9. concentrationconcentrated under vacuum
  10. customPurification by silica gel column chromatography (0-10% EtOAc in DCM)

Sources & evidence

ORD record
ord-01d0f3d7fac142b39a5d3f1e8fc6acac
Source dataset
uspto-grants-2014_12
Patent number
US08912219B2

Reaction notes

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