Hydrogen Peroxide → HCID 178493727, compound

HRID 1669072Notes

Reaction equation

HRID 1669072 reaction equation
OO.C(OC(C(F)(F)F)=O)(C(F)(F)F)=[O:4].[CH3:16][O:17][CH:18]1[CH2:21][N:20]([CH2:22][CH2:23][CH2:24][C:25]2[N:26]=[N+:27]([O-:38])[C:28]3[CH:37]=[C:36]4[C:32]([CH2:33][CH2:34][CH2:35]4)=[CH:31][C:29]=3[N:30]=2)[CH2:19]1.C(O)(C(F)(F)F)=O>C(Cl)Cl.N>[CH3:16][O:17][CH:18]1[CH2:21][N:20]([CH2:22][CH2:23][CH2:24][C:25]2[N:26]=[N+:27]([O-:38])[C:28]3[CH:37]=[C:36]4[C:32]([CH2:33][CH2:34][CH2:35]4)=[CH:31][C:29]=3[N+:30]=2[O-:4])[CH2:19]1

Participants

7

Reactant 4

HCID 784Hydrogen PeroxideHCID 6422Trifluoroacetic acidHCID 9845Trifluoroacetic anhydrideHCID 11951998HCID 11951998, compound

Product 1

HCID 178493727HCID 178493727, compoundYield 60.5%

Reagents, catalysts & solvents 2

HCID 222AmmoniaSolventHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

H2O2 (70%, 2.0 mL, 39 mmol) was added dropwise to a stirred solution of TFAA (5.4 mL, 39 mmol) in DCM (50 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 82 (0.93 g, 3.0 mmol) and TFA (1.5 mL, 19.5 mmol) in DCM (50 mL) at 0° C. The solution was stirred at 20° C. for 8 h, diluted with dilute aqueous NH3 solution (30 mL) and extracted with DCM (3×150 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 83 (0.60 g, 60%) as a red gum: 1H NMR δ 8.31 (s, 1H, H-9), 8.28 (s, 1H, H-5), 4.60-4.70 (m, 2H, CH2N), 4.33-4.40 (m, 1H, CHO), 3.60-3.75 (m, 2H, CH2N), 3.33 (s, 3H, CH3O), 3.25-3.32 (m, 2H, CH2N), 3.12-3.25 (m, 6H, H-6, H-8, CH2), 2.27-2.33 (m, 4H, H-7, CH2); 13C NMR δ 155.5, 152.3, 151.2, 139.1, 134.1, 115.9, 113.9, 67.8, 61.0, 58.9, 56.9, 55.6, 32.9, 32.4, 26.9, 25.6, 22.9; HRMS (FAB+) calcd for C17H23N4O3 (MH+) m/z 331.1770, found 331.1771.

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 (3×150 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-7e871e28a1d74911875c44ab92721c70
Source dataset
uspto-grants-2011_08
Patent number
US07989451B2

Reaction notes

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