Hydrogen Peroxide → HCID 178526291, compound

HRID 1669076Notes

Reaction equation

HRID 1669076 reaction equation
OO.C(OC(C(F)(F)F)=O)(C(F)(F)F)=[O:4].[N:16]1([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)[CH2:21][CH2:20][CH2:19][CH2:18][CH2:17]1.C(O)(C(F)(F)F)=O>C(Cl)Cl.N>[N:16]1([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])[CH2:17][CH2:18][CH2:19][CH2:20][CH2:21]1

Participants

7

Reactant 4

HCID 784Hydrogen PeroxideHCID 6422Trifluoroacetic acidHCID 9845Trifluoroacetic anhydrideHCID 11952002HCID 11952002, compound

Product 1

HCID 178526291HCID 178526291, compoundYield 76.1%

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 86 (1.33 g, 4.2 mmol) and TFA (1.5 mL, 19.5 mmol) in DCM (50 mL) at 0° C. The solution was stirred at 0° C. for 4 h, diluted with dilute aqueous NH3 solution (40 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 87 (1.05 g, 76%) as a red gum: 1H NMR δ 8.30 (s, 1H, H-9), 8.26 (s, 1H, H-5), 3.34-3.40 (m, 4H, 2×CH2), 3.27 (t, J=7.1 Hz, 2H, CH2N), 3.12-3.21 (m, 4H, H-6, H-8), 3.05-3.12 (m, 2H, CH2), 2.42-2.51 (m, 2H, CH2), 2.22-2.32 (m, 2H, H-7), 1.64-1.73 (m, 4H, 2×CH2), 1.40-1.51 (m, 2H, CH2); 13C NMR δ 161.8, 155.2, 150.8, 139.1, 134.0, 115.8, 113.9, 58.9, 53.7, 53.4, 33.4, 32.9, 28.0, 25.6, 24.0 (2), 19.7, 13.6; HRMS (FAB+) calcd for C18H25N4O2 (MH+) m/z 329.1974, found 329.1974.

Workup

  1. temperaturewarmed to 20° C. for 10 min
  2. temperaturecooled to 0° C.
  3. stirringThe solution was stirred at 0° C. for 4 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-ecc78fecab6449bdad26016a24c9fb4d
Source dataset
uspto-grants-2011_08
Patent number
US07989451B2

Reaction notes

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