Ammonium Chloride → (+/-)-2-Azido-6-methyl-4-(3-nitropyridin-4-yl)cyclohex-3-enol

HRID 2192570Notes

Reaction equation

HRID 2192570 reaction equation
[CH3:1][CH:2]1[CH2:7][C:6]([C:8]2[CH:13]=[CH:12][N:11]=[CH:10][C:9]=2[N+:14]([O-:16])=[O:15])=[CH:5][CH:4]=[CH:3]1.C1C=C(Cl)C=C(C(OO)=[O:25])C=1.[N-:28]=[N+:29]=[N-:30].[Na+].[Cl-].[NH4+]>C(Cl)Cl.C(O)C.O>[N:28]([CH:4]1[CH:5]=[C:6]([C:8]2[CH:13]=[CH:12][N:11]=[CH:10][C:9]=2[N+:14]([O-:16])=[O:15])[CH2:7][CH:2]([CH3:1])[CH:3]1[OH:25])=[N+:29]=[N-:30]

Participants

8

Reactant 4

HCID 25517Ammonium ChlorideHCID 33557Sodium AzideHCID 70297m-Chloroperbenzoic acidHCID 59226560HCID 59226560, compound

Product 1

HCID 72238239(+/-)-2-Azido-6-methyl-4-(3-nitropyridin-4-yl)cyclohex-3-enolYield 49%

Reagents, catalysts & solvents 3

HCID 702EthanolSolventHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

To a solution of (+/−)-4-(5-methylcyclohexa-1,3-dienyl)-3-nitropyridine (1.0 equiv.) in DCM (0.1 M) at 0° C. was added m-CPBA (1.1 equiv.) and the reaction was allowed to warm to room temperature. After 3 hours, the mixture was quenched with saturated NaHCO3, extracted with DCM, and the organic phase was dried with sodium sulfate, filtered, and concentrated to give a yellow oil. The crude was dissolved in ethanol and water (3:1, 0.1 M), and sodium azide (2.0 equiv.) and ammonium chloride (2.0 equiv.) were added. The reaction was stirred for 4 hours, then concentrated in vacuo. To the crude was added ethyl acetate and water, the organic phase was washed with brine, dried with sodium sulfate, filtered, and concentrated. The crude material was purified via silica gel column chromatography eluting with ethyl acetate and hexanes (1:1) to afford (+/−)-2-azido-6-methyl-4-(3-nitropyridin-4-yl)cyclohex-3-enol as an oil in 49% yield. LC/MS=276.1 (M+H), Rt=0.71 min.

Workup

  1. customthe mixture was quenched with saturated NaHCO3
  2. extractionextracted with DCM
  3. dry with materialthe organic phase was dried with sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customto give a yellow oil
  7. concentrationconcentrated in vacuo
  8. additionTo the crude was added ethyl acetate and water
  9. washthe organic phase was washed with brine
  10. dry with materialdried with sodium sulfate
  11. filtrationfiltered
  12. concentrationconcentrated
  13. customThe crude material was purified via silica gel column chromatography
  14. washeluting with ethyl acetate and hexanes (1:1)

Sources & evidence

ORD record
ord-669a21627d1f42f292ab4f070bb72449
Source dataset
uspto-grants-2012_12
Patent number
US08329732B2

Reaction notes

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