Hydrogen Peroxide → HCID 135899483, compound

HRID 1669171Notes

Reaction equation

HRID 1669171 reaction equation
OO.C(OC(C(F)(F)F)=O)(C(F)(F)F)=[O:4].[CH3:16][N:17]([CH3:36])[CH2:18][CH2:19][NH:20][C:21]1[N:22]=[N+:23]([O-:35])[C:24]2[C:34]3[CH2:33][CH2:32][CH2:31][O:30][C:29]=3[CH:28]=[CH:27][C:25]=2[N:26]=1.C(O)(C(F)(F)F)=O>C(Cl)Cl.N>[O-:35][N+:23]1[C:24]2[C:34]3[CH2:33][CH2:32][CH2:31][O:30][C:29]=3[CH:28]=[CH:27][C:25]=2[N+:26]([O-:4])=[C:21]([NH:20][CH2:19][CH2:18][N:17]([CH3:36])[CH3:16])[N:22]=1

Participants

7

Reactant 4

HCID 784Hydrogen PeroxideHCID 6422Trifluoroacetic acidHCID 9845Trifluoroacetic anhydrideHCID 25139886HCID 25139886, compound

Product 1

HCID 135899483HCID 135899483, compoundYield 54%

Reagents, catalysts & solvents 2

HCID 222AmmoniaSolventHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

H2O2 (70%, 0.16 mL, ca. 3.2 mmol) was added dropwise to a stirred solution of TFAA (0.45 mL, 3.2 mmol) in DCM (10 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 236 (50 mg, 0.17 mmol) and TFA (0.12 mL, 1.6 mmol) in DCM (15 mL) at 0° C. The solution was stirred at 20° 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 237 (28 mg, 54%) as a red gum: 1H NMR δ 8.11 (d, J=9.5 Hz, 1H, H-5), 7.36 (d, J=9.5 Hz, 1H, H-6), 7.23 (br s, 1H, NH), 4.21-4.25 (m, 2H, H-8), 3.61 (br t, J=5.8 Hz, 2H, CH2N), 3.56 (br t, J=6.5 Hz, 2H, H-10), 2.62 (br t, J=6.0 Hz, 2H, CH2N), 2.31 [s, 6H, N(CH3)2], 2.00-2.07 (m, 2H, H-9); 13C NMR δ 154.0, 148.4, 135.8, 130.6, 128.9, 116.0, 114.9, 66.2, 57.5, 45.1 (2), 38.7, 24.5, 21.9; MS (FAB+) m/z 306 (MH+, 60%), 290 (20), 176 (100); HRMS (FAB+) calcd for C14H20N5O3 (MH+) m/z 306.1566, found 306.1568. Anal. calcd for C14H19N5O3.½H2O.½MeOH: C, 52.7; H, 6.7; N, 21.2. Found: C, 52.8; H, 6.7; N, 21.2%.

Workup

  1. temperaturewarmed to 20° C. for 10 min
  2. temperaturecooled to 0° C.
  3. stirringThe solution was stirred at 20° 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-bc09334421ec43efa24751ea1f2b9038
Source dataset
uspto-grants-2011_08
Patent number
US07989451B2

Reaction notes

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