Hydrogen Peroxide → HCID 178421797, compound

HRID 1669090Notes

Reaction equation

HRID 1669090 reaction equation
OO.C(OC(C(F)(F)F)=O)(C(F)(F)F)=[O:4].[CH3:16][CH:17]1[CH2:39][C:38]2[C:19](=[CH:20][C:21]3[N+:26]([O-:27])=[N:25][C:24]([CH2:28][CH2:29][CH2:30][N:31]4[CH2:36][CH2:35][O:34][CH2:33][CH2:32]4)=[N:23][C:22]=3[CH:37]=2)[CH2:18]1.C(O)(C(F)(F)F)=O>C(Cl)Cl.N>[CH3:16][CH:17]1[CH2:39][C:38]2[C:19](=[CH:20][C:21]3[N+:26]([O-:27])=[N:25][C:24]([CH2:28][CH2:29][CH2:30][N:31]4[CH2:32][CH2:33][O:34][CH2:35][CH2:36]4)=[N+:23]([O-:4])[C:22]=3[CH:37]=2)[CH2:18]1

Participants

7

Reactant 4

HCID 784Hydrogen PeroxideHCID 6422Trifluoroacetic acidHCID 9845Trifluoroacetic anhydrideHCID 11952185HCID 11952185, compound

Product 1

HCID 178421797HCID 178421797, compoundYield 44%

Reagents, catalysts & solvents 2

HCID 222AmmoniaSolventHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

H2O2 (70%, 0.49 mL, ca. 9.7 mmol) was added dropwise to a stirred solution of TFAA (1.4 mL, 9.7 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 102 (320 mg, 1.0 mmol) and TFA (0.38 mL, 4.9 mmol) in DCM (20 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 (4×30 mL). The combined organic fraction was dried and the solvent evaporated. The residue was purified by chromatography, eluting with a gradient (0-5%) of MeOH/DCM, to give 1,4-dioxide 104 (148 mg, 44%) as a red solid: mp (MeOH/DCM) 119-121° C.; 1H NMR δ 8.27 (s, 1H, H-9), 8.23 (s, 1H, H-5), 3.45 (br t, J=4.5 Hz, 4H, 2×CH2O), 3.21-3.33 (m, 4H, 2×CH2), 2.68-2.81 (m, 3H, H-7, CH2), 2.48 (t, J=6.5 Hz, 2H, CH2N), 2.37 (br t, J=4.5 Hz, 4H, 2×CH2N), 2.06-2.13 (m, 2H, CH2), 1.20 (d, J=6.4 Hz, 3H, CH3); 13C NMR δ 155.2, 154.7, 150.2, 139.1, 133.8, 115.9, 113.9, 67.0 (2), 58.0, 53.5 (2), 41.4, 40.8, 35.0, 28.8, 21.8, 20.1. Anal. calcd for C18H24N4O3.¼CH3OH: C, 62.2; H, 7.2; N, 15.9. Found: C, 62.3; H, 7.0; N, 16.0%.

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 (4×30 mL)
  5. customThe combined organic fraction was dried
  6. customthe solvent evaporated
  7. customThe residue was purified by chromatography
  8. washeluting with a gradient (0-5%) of MeOH/DCM

Sources & evidence

ORD record
ord-7200273db53b4016aec4b7eecd1d06ff
Source dataset
uspto-grants-2011_08
Patent number
US07989451B2

Reaction notes

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