Hydrogen Peroxide → 6-Fluoro-3-methyl-quinoline 1-oxide

HRID 2281131Notes

Reaction equation

HRID 2281131 reaction equation
[F:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[N:8]=[CH:7][C:6]([CH3:12])=[CH:5]2.OO.[O-:15]S([O-])=O.[Na+].[Na+].[I-].[Na+]>C(O)(=O)C>[F:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[N+:8]([O-:15])=[CH:7][C:6]([CH3:12])=[CH:5]2

Participants

6

Reactant 4

HCID 784Hydrogen PeroxideHCID 5238Sodium IodideHCID 24437Sodium SulfiteHCID 157236166-Fluoro-3-methylquinoline2×

Product 1

HCID 867188376-Fluoro-3-methyl-quinoline 1-oxide

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Conditions

Temperature
80 °C

Procedure

6-Fluoro-3-methyl-quinoline (Intermediate 28) (48.0 mg, 0.298 mmol) was dissolved in acetic acid (1 mL) and 30% aqueous H2O2 (0.040 mL, 0.396 mmol) was added. This was stirred at 80° C. for 16 h before cooling. A few mLs of a 10% aq. solution of Na2SO3 was added followed by a spatula tip of sodium iodide. This was stirred for 10 min before partitioning between ethyl acetate and sat. NaHCO3. The separated aqueous layer was extracted with ethyl acetate and the combined organics dried over MgSO4. Purification by silica gel flash chromatography (methanol/ethyl acetate) gave 6-fluoro-3-methyl-quinoline 1-oxide (29.4 mg) as a white solid. 1H NMR (400 MHz, CDCl3) δ 8.72 (dd, J=9.4, 5.3 Hz, 1 H) 8.38 (s, 1 H) 7.36-7.50 (m, 3 H) 2.46 (s, 3 H); MS (M+1): 178.1.

Workup

  1. temperaturebefore cooling
  2. stirringThis was stirred for 10 min
  3. custombefore partitioning between ethyl acetate and sat. NaHCO3
  4. extractionThe separated aqueous layer was extracted with ethyl acetate
  5. dry with materialthe combined organics dried over MgSO4
  6. customPurification by silica gel flash chromatography (methanol/ethyl acetate)

Sources & evidence

ORD record
ord-1b55340e704445fba7785b65e5b6ba78
Source dataset
uspto-grants-2015_09
Patent number
US09139538B2

Reaction notes

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