Hydrogen Peroxide → HCID 135899492, compound

HRID 1669187Notes

Reaction equation

HRID 1669187 reaction equation
OO.C(OC(C(F)(F)F)=O)(C(F)(F)F)=[O:4].[CH2:16]([NH:18][C:19]1[N:20]=[N+:21]([O-:34])[C:22]2[C:31]([N:32]=1)=[CH:30][C:29]1[CH2:28][N:27]([CH3:33])[CH2:26][CH2:25][C:24]=1[CH:23]=2)[CH3:17].C(O)(C(F)(F)F)=O>C(Cl)Cl.N>[CH2:16]([NH:18][C:19]1[N:20]=[N+:21]([O-:34])[C:22]2[C:31]([N+:32]=1[O-:4])=[CH:30][C:29]1[CH2:28][N:27]([CH3:33])[CH2:26][CH2:25][C:24]=1[CH:23]=2)[CH3:17]

Participants

7

Reactant 4

HCID 784Hydrogen PeroxideHCID 6422Trifluoroacetic acidHCID 9845Trifluoroacetic anhydrideHCID 25139025HCID 25139025, compound

Product 1

HCID 135899492HCID 135899492, compoundYield 8%

Reagents, catalysts & solvents 2

HCID 222AmmoniaSolventHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
20 °C

Procedure

H2O2 (70%, 1.7 mL, ca. 17 mmol) was added dropwise to a stirred solution of TFAA (2.4 mL, 17 mmol) in DCM (15 mL) at 0° C. The solution was stirred at 20° C. for 10 min, then cooled to 0° C., added to a solution of 1-oxide 258 (440 mg, 1.7 mmol) and TFA (0.66 mL, 8.5 mmol) in DCM (15 mL) at 0° C. The solution was stirred at 20° C. for 4 h, diluted with dilute aqueous NH3 solution (80 mL) and extracted with DCM (4×125 mL). The combined organic fraction was dried and the solvent evaporated. The residue was purified by chromatography, eluting with a gradient (1-10%) of MeOH/DCM, to give 1,4-dioxide 259 (35 mg, 8%) as a red solid: mp 120-124° C.; 1H NMR δ 8.10 (s, 1H, H-10), 7.96 (s, 1H, H-5), 6.95 (br s, 1H, NH), 3.78 (s, 2H, H-6), 3.63 (dq, J=7.2, 6.0 Hz, 2H, CH2N), 3.10 (t, J=6.0 Hz, 2H, H-8), 2.75 (t, J=6.0 Hz, 2H, H-9), 2.50 (s, 3H, NCH3), 1.36 (t, J=7.2 Hz, 3H, CH3); 13C NMR δ 149.3, 145.5, 136.5, 135.3, 129.3, 120.5, 113.9, 58.1, 52.1, 45.8, 36.5, 29.1, 14.8; MS (APCI) m/z 276. (MH+, 100%); HRMS (FAB+) calcd for C13H18N5O2 (MH+) m/z 276.1461, found 276.1456.

Workup

  1. temperaturecooled to 0° C.
  2. stirringThe solution was stirred at 20° C. for 4 h
  3. extractionextracted with DCM (4×125 mL)
  4. customThe combined organic fraction was dried
  5. customthe solvent evaporated
  6. customThe residue was purified by chromatography
  7. washeluting with a gradient (1-10%) of MeOH/DCM

Sources & evidence

ORD record
ord-ea83134bf8f04eaf93d2014c5a96d208
Source dataset
uspto-grants-2011_08
Patent number
US07989451B2

Reaction notes

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