Hydrogen Peroxide → HCID 178438079, compound

HRID 1669192Notes

Reaction equation

HRID 1669192 reaction equation
OO.[CH2:3]([C:5]1[N:6]=[N+:7]([O-:20])[C:8]2[C:17]3[CH2:16][N:15]([CH3:18])[CH2:14][CH2:13][C:12]=3[CH:11]=[CH:10][C:9]=2[N:19]=1)[CH3:4].C(O)(C(F)(F)F)=[O:22]>C(Cl)Cl.N>[CH2:3]([C:5]1[N:6]=[N+:7]([O-:20])[C:8]2[C:17]3[CH2:16][N:15]([CH3:18])[CH2:14][CH2:13][C:12]=3[CH:11]=[CH:10][C:9]=2[N+:19]=1[O-:22])[CH3:4]

Participants

6

Reactant 3

HCID 784Hydrogen PeroxideHCID 6422Trifluoroacetic acidHCID 25139616HCID 25139616, compound

Product 1

HCID 178438079HCID 178438079, compoundYield 19%

Reagents, catalysts & solvents 2

HCID 222AmmoniaSolventHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
20 °C

Procedure

H2O2 (70%, 0.5 mL, ca. 5 mmol) was added dropwise to a stirred solution of TFM (0.7 mL, 5 mmol) in DCM (10 mL) at 0° C. The solution was stirred at 20° C. for 10 min, then cooled to 0° C., added to a solution of 1-oxide 264 (120 mg, 0.5 mmol) and TFA (0.19 mL, 2.5 mmol) in DCM (10 mL) at 0° C. The solution was stirred at 20° C. for 4 h, diluted with dilute aqueous NH3 solution (20 mL) and extracted with DCM (4×100 mL). The combined organic fraction was dried and the solvent evaporated. The residue was purified by chromatography, eluting with a gradient (2-8%) of MeOH/DCM, to give 1,4-dioxide 265 (24 mg, 19%) as a red solid: mp 117-121° C.; 1H NMR δ 8.35 (d, J=8.8 Hz, 1H, H-5), 7.70 (d, J=8.8 Hz, 1H, H-6), 4.41 (s, 2H, H-10), 3.18 (q, J=7.5 Hz, 2H, CH2), 3.12 (br t, J=5.8 Hz, 2H, H-7), 2.74 (t, J=5.8 Hz, 2H, H-8), 2.58 (s, 3H, NCH3), 1.42 (t, J=7.5 Hz, 3H, CH3); MS (APCI) m/z 261 (MH+, 100%); HRMS (FAB+) calcd for C13H17N4O2 (MH+) m/z 261.1352, found: 261.1354.

Workup

  1. temperaturecooled to 0° C.
  2. stirringThe solution was stirred at 20° C. for 4 h
  3. extractionextracted with DCM (4×100 mL)
  4. customThe combined organic fraction was dried
  5. customthe solvent evaporated
  6. customThe residue was purified by chromatography
  7. washeluting with a gradient (2-8%) of MeOH/DCM

Sources & evidence

ORD record
ord-c76e8cf82402470192b061e369491464
Source dataset
uspto-grants-2011_08
Patent number
US07989451B2

Reaction notes

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