Hydrogen Peroxide → HCID 178526290, compound

HRID 1669074Notes

Reaction equation

HRID 1669074 reaction equation
OO.C(OC(C(F)(F)F)=O)(C(F)(F)F)=[O:4].[N:16]1([CH2:21][CH2:22][CH2:23][C:24]2[N:25]=[N+:26]([O-:37])[C:27]3[CH:36]=[C:35]4[C:31]([CH2:32][CH2:33][CH2:34]4)=[CH:30][C:28]=3[N:29]=2)[CH2:20][CH2:19][CH2:18][CH2:17]1.C(O)(C(F)(F)F)=O>C(Cl)Cl.N>[N:16]1([CH2:21][CH2:22][CH2:23][C:24]2[N:25]=[N+:26]([O-:37])[C:27]3[CH:36]=[C:35]4[C:31]([CH2:32][CH2:33][CH2:34]4)=[CH:30][C:28]=3[N+:29]=2[O-:4])[CH2:20][CH2:19][CH2:18][CH2:17]1

Participants

7

Reactant 4

HCID 784Hydrogen PeroxideHCID 6422Trifluoroacetic acidHCID 9845Trifluoroacetic anhydrideHCID 11952000HCID 11952000, compound

Product 1

HCID 178526290HCID 178526290, compoundYield 58.5%

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 84 (1.50 g, 4.6 mmol) and TFA (1.5 mL, 19.5 mmol) in DCM (50 mL) at 0° C. The solution was stirred at 20° C. for 6 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 85 (846 mg, 35%) as a red gum: 1H NMR δ 8.25 (s, 1H, H-9), 8.20 (s, 1H, H-5), 3.22-3.22 (m, 6H, 3×CH2), 3.11-3.20 (m, 4H, H-6, H-8), 2.80-3.05 (m, 2H, CH2), 2.33-2.43 (m, 2H, CH2), 2.21-2.30 (m, 2H, H-7), 2.13 (br s, 4H, 2×CH2); 13C NMR δ 155.4, 152.4, 151.0, 139.0, 133.9, 115.7, 113.7, 54.2, 53.5 (2), 33.3, 32.8, 27.1, 25.4, 23.8, 23.2 (2); HRMS (FAB+) calcd for C17H23N4O2 (MH+) m/z 315.1821, found 315.1820.

Workup

  1. temperaturewarmed to 20° C. for 10 min
  2. temperaturecooled to 0° C.
  3. stirringThe solution was stirred at 20° C. for 6 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-970870dd195c45fa8f179dfe7db9630c
Source dataset
uspto-grants-2011_08
Patent number
US07989451B2

Reaction notes

Loading…