Hydrogen Peroxide → HCID 135502643, compound

HRID 1160634Notes

Reaction equation

HRID 1160634 reaction equation
OO.FC(F)(F)C(OC(=O)C(F)(F)F)=[O:6].[CH2:16]([O:18][C:19]1[CH:20]=[CH:21][C:22]2[N+:27]([O-:28])=[N:26][C:25]([NH:29][CH2:30][CH2:31][N:32]([CH3:34])[CH3:33])=[N:24][C:23]=2[CH:35]=1)[CH3:17].FC(F)(F)C(O)=O>C(Cl)Cl.N>[CH2:16]([O:18][C:19]1[CH:20]=[CH:21][C:22]2[N+:27]([O-:28])=[N:26][C:25]([NH:29][CH2:30][CH2:31][N:32]([CH3:34])[CH3:33])=[N+:24]([O-:6])[C:23]=2[CH:35]=1)[CH3:17]

Participants

7

Reactant 4

HCID 784Hydrogen PeroxideHCID 6422Trifluoroacetic acidHCID 9845Trifluoroacetic anhydrideHCID 24741740HCID 24741740, compound

Product 1

HCID 135502643HCID 135502643, compoundYield 31%

Reagents, catalysts & solvents 2

HCID 222AmmoniaSolventHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
5 °C

Procedure

Hydrogen peroxide (70%, 0.7 mL, ca. 13.9 mmol) was added dropwise to a stirred solution of trifluoroacetic anhydride (2.0 mL, 13.9 mmol) in DCM (20 mL) at 5° C. The mixture was stirred at 5° C. for 5 min, warmed to 20° C., stirred for 10 min, and cooled to 5° C. The mixture was added to a stirred solution of 1-oxide 18 (385 mg, 1.4 mmol) and trifluoroacetic acid (0.53 mL, 6.9 mmol) in DCM (20 mL) at 5° C. and the mixture stirred at 20° C. for 6 h. The solution was carefully diluted with dil. aq. NH3 solution (20 mL) and the mixture extracted with CHCl3 (5×50 mL). The organic fraction was dried and the solvent evaporated. The residue was chromatographed, eluting with a gradient (0-10%) of MeOH/DCM, to give 1,4-dioxide 19 (125 mg, 31%) as a red solid, mp (MeOH/EtOAc) 150-152° C.; 1H NMR 8.23 (d, J=9.6 Hz, 1 H, H-8), 7.48 (d, J=2.6 Hz, 1 H, H-5), 7.46 (brs, 1 H, NH), 7.03 (dd, J=9.6, 2.6 Hz, 1 H, H-7), 4.25 (q, J=7.0 Hz, 2 H, CH2O), 3.64 (br dd, J=6.0, 5.9 Hz, 2 H, CH2N), 2.61 (t, J=6.0 Hz, 2 H, CH2N), 2.30 [s, 6 H, (CH3)2], 1.49 (t, J=7.0 Hz, 3 H, CH3); 13C NMR δ 165.5, 150.2, 140.3, 125.6, 123.5, 120.6, 95.4, 65.4, 57.5, 45.2 (2), 35.9, 14.3; MS (FAB+) m/z 294 (MH+, 100%), 278 (30), 276 (20); HRMS (FAB+) calcd for C13H19N5O3 (MH+) m/z 294.1566, found 294.1568. Anal. Calcd for C13H19N5O3: C, 53.2; H, 6.5; N, 23.9. Found: C, 53.1; H, 6.3; N, 23.6%.

Workup

  1. temperaturewarmed to 20° C.
  2. stirringstirred for 10 min
  3. temperaturecooled to 5° C
  4. stirringthe mixture stirred at 20° C. for 6 h
  5. extractionthe mixture extracted with CHCl3 (5×50 mL)
  6. customThe organic fraction was dried
  7. customthe solvent evaporated
  8. customThe residue was chromatographed
  9. washeluting with a gradient (0-10%) of MeOH/DCM

Sources & evidence

ORD record
ord-c0f6c951fecd4d80891dbb60bad9c683
Source dataset
uspto-grants-2010_10
Patent number
US07816521B2

Reaction notes

Loading…