Hydrogen Peroxide → HCID 178483401, compound

HRID 1669068Notes

Reaction equation

HRID 1669068 reaction equation
OO.C(OC(C(F)(F)F)=O)(C(F)(F)F)=[O:4].[CH3:16][N:17]([CH3:35])[CH2:18][CH2:19][CH2:20][C:21]1[N:22]=[N+:23]([O-:34])[C:24]2[CH:33]=[C:32]3[C:28]([CH2:29][CH2:30][CH2:31]3)=[CH:27][C:25]=2[N:26]=1.C(O)(C(F)(F)F)=O>C(Cl)Cl.N>[O-:34][N+:23]1[C:24]2[CH:33]=[C:32]3[C:28](=[CH:27][C:25]=2[N+:26]([O-:4])=[C:21]([CH2:20][CH2:19][CH2:18][N:17]([CH3:16])[CH3:35])[N:22]=1)[CH2:29][CH2:30][CH2:31]3

Participants

7

Reactant 4

HCID 784Hydrogen PeroxideHCID 6422Trifluoroacetic acidHCID 9845Trifluoroacetic anhydrideHCID 67334083HCID 67334083, compound

Product 1

HCID 178483401HCID 178483401, compoundYield 41.1%

Reagents, catalysts & solvents 2

HCID 222AmmoniaSolventHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

H2O2 (70%, 0.65 mL, 13 mmol) was added dropwise to a stirred solution of TFAA (1.8 mL, 13 mmol) in DCM (20 mL) at 0° C. The solution was stirred at 0° C. for 5 min, warmed to 20° C. for 10 min, then cooled to 0° C. and added to a stirred solution of 1-oxide 78 (353 mg, 1.3 mmol) and TFA (0.7 mL, 9.1 mmol) in DCM (20 mL) at 0° C. The solution was stirred at 20° C. for 8 h, diluted with dilute aqueous NH3 solution (12 mL) and extracted with DCM (4×50 mL). The combined organic fraction was dried and the solvent evaporated. The residue was purified by chromatography, eluting with a gradient (0-10%) of MeOH/DCM, to give 1,4-dioxide 79 (154 mg, 41%) as a red solid: 1H NMR δ 8.30 (s, 1H, H-9), 8.26 (s, 1H, H-5), 3.25-3.09 (m, 6H, H-6, H-8, CH2), 2.75 (t, J=7.3 Hz, 2H, CH2), 2.70 [s, 6H, N(CH3)2], 2.29-2.14 (m, 4H, H-7, CH2); 13C NMR δ 155.2, 153.9, 150.8, 139.1, 133.9, 115.9, 113.9, 58.0, 44.3 (2), 33.4, 32.9, 27.9, 25.6, 21.7; HRMS (FAB+) calcd for C15H21N4O2 (MH+) m/z 289.1665, found 289.1669.

Workup

  1. temperaturewarmed to 20° C. for 10 min
  2. temperaturecooled to 0° C.
  3. stirringThe solution was stirred at 20° C. for 8 h
  4. extractionextracted with DCM (4×50 mL)
  5. customThe combined organic fraction was dried
  6. customthe solvent evaporated
  7. customThe residue was purified by chromatography
  8. washeluting with a gradient (0-10%) of MeOH/DCM

Sources & evidence

ORD record
ord-4441bf779aca4cf78ba56c5ac313c248
Source dataset
uspto-grants-2011_08
Patent number
US07989451B2

Reaction notes

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