Hydrogen Peroxide → HCID 135526540, compound

HRID 1669015Notes

Reaction equation

HRID 1669015 reaction equation
OO.C(OC(C(F)(F)F)=O)(C(F)(F)F)=[O:4].[O-:16][N+:17]1[C:22]2[CH:23]=[C:24]3[C:28](=[CH:29][C:21]=2[N:20]=[C:19]([NH:30][CH2:31][CH2:32][N:33]([CH2:36][CH3:37])[CH2:34][CH3:35])[N:18]=1)[CH2:27][CH2:26][CH2:25]3.C(O)(C(F)(F)F)=O>C(Cl)Cl.N>[O-:16][N+:17]1[C:22]2[CH:23]=[C:24]3[C:28](=[CH:29][C:21]=2[N+:20]([O-:4])=[C:19]([NH:30][CH2:31][CH2:32][N:33]([CH2:36][CH3:37])[CH2:34][CH3:35])[N:18]=1)[CH2:27][CH2:26][CH2:25]3

Participants

7

Reactant 4

HCID 784Hydrogen PeroxideHCID 6422Trifluoroacetic acidHCID 9845Trifluoroacetic anhydrideHCID 11950762HCID 11950762, compound

Product 1

HCID 135526540HCID 135526540, compoundYield 56.4%

Reagents, catalysts & solvents 2

HCID 222AmmoniaSolventHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

H2O2 (70%, 0.52 mL, ca. 10.4 mmol) was added dropwise to a stirred solution of TFAA (1.5 mL, 10.4 mmol) in DCM (15 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 26 (312 mg, 1.0 mmol) and TFA (0.40 mL, 5.2 mmol) in DCM (20 mL) at 0° C. The solution was stirred at 5° C. for 4 h, diluted with dilute aqueous NH3 solution (10 mL) and extracted with CHCl3 (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 27 (179 mg, 54%) as a red gum: 1H NMR δ 8.11 (br s, 2H, H-5, H-9), 7.73 (br s, 1H, NH), 3.64-3.69 (m, 2H, CH2N), 3.01-3.10 (m, 4H, H-6, H-8), 2.81-2.85 (m, 2H, CH2N), 2.64-2.73 (m, 4H, 2×CH2N), 2.14-2.22 (m, 2H, H-7), 1.09 (t, J=7.1 Hz, 6H, 2×CH3); 13C NMR δ 156.0, 149.5, 145.8, 138.1, 129.8, 115.7, 111.7, 51.1, 46.6 (2), 38.5, 33.4, 32.3, 25.6, 11.0 (2); MS (FAB+) m/z 318 (MH+, 70%), 302 (20); HRMS (FAB+) calcd for C16H24N5O2 (MH+) m/z 318.1930, found 318.1933.

Workup

  1. temperaturewarmed to 20° C. for 10 min
  2. temperaturecooled to 0° C.
  3. stirringThe solution was stirred at 5° C. for 4 h
  4. extractionextracted with CHCl3 (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-181b1842fcfb4db4b5ed6f249bf4fd96
Source dataset
uspto-grants-2011_08
Patent number
US07989451B2

Reaction notes

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