Hydrogen Peroxide → HCID 135899515, compound

HRID 1669149Notes

Reaction equation

HRID 1669149 reaction equation
OO.[N:3]1([CH2:9][CH2:10][CH2:11][NH:12][C:13]2[N:14]=[N+:15]([O-:26])[C:16]3[CH:22]=[C:21]4[O:23][CH2:24][CH2:25][C:20]4=[CH:19][C:17]=3[N:18]=2)[CH2:8][CH2:7][O:6][CH2:5][CH2:4]1.C(O)(C(F)(F)F)=[O:28]>C(Cl)Cl.N>[N:3]1([CH2:9][CH2:10][CH2:11][NH:12][C:13]2[N:14]=[N+:15]([O-:26])[C:16]3[CH:22]=[C:21]4[O:23][CH2:24][CH2:25][C:20]4=[CH:19][C:17]=3[N+:18]=2[O-:28])[CH2:8][CH2:7][O:6][CH2:5][CH2:4]1

Participants

6

Reactant 3

HCID 784Hydrogen PeroxideHCID 6422Trifluoroacetic acidHCID 25139752HCID 25139752, compound

Product 1

HCID 135899515HCID 135899515, compoundYield 14%

Reagents, catalysts & solvents 2

HCID 222AmmoniaSolventHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
20 °C

Procedure

H2O2 (70%, 1.6 mL, ca. 32 mmol) was added dropwise to a stirred solution of TFM (4.5 mL, 32 mmol) in DCM (40 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 199 (1.06 g, 3.2 mmol) and TFA (1.25 mL, 16 mmol) in DCM (40 mL) at 0° C. The solution was stirred at 20° C. for 4.5 h, diluted with dilute aqueous NH3 solution (50 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 (0-10%) of MeOH/DCM to give 1,4-dioxide 200 (150 mg, 14%) as a red solid: mp 145-148° C.; 1H NMR δ 8.26 (br s, 1H, NH), 8.14 (s, 1H, H-9), 7.53 (s, 1H, H-5), 4.74 (t, J=8.3 Hz, 2H, H-7), 3.83 (t, J=4.6 Hz, 4H, 2×CH2O), 3.65 (br q, J=5.9 Hz, 2H, CH2N), 3.43 (dt, J=8.3, 1.2 Hz, 2H, H-6), 2.58 (br t, J=6.1 Hz, 2H, CH2), 2.53 (br s, 4H, 2×CH2N), 1.88 (p, J=6.2 Hz, 2H, CH2); 13C NMR δ 159.8, 149.0, 141.5, 135.2, 130.8, 113.1, 97.4, 72.4, 66.8 (2), 57.7, 53.8 (2), 41.6, 29.7, 24.5; MS (APCI) m/z 348 (MH+, 100%); HRMS (FAB+) calcd for C16H22N5O4 (MH+) m/z 348.1672, found 348.1666. Anal. calcd for C16H21N5O4.0.4CH2Cl2: C, 51.7; H, 5.8; N, 18.4. Found: C, 51.7; H, 5.4; N, 18.1%.

Workup

  1. temperaturecooled to 0° C.
  2. stirringThe solution was stirred at 20° C. for 4.5 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 (0-10%) of MeOH/DCM

Sources & evidence

ORD record
ord-e27814b7ebe141148c14ffaec3bee6f8
Source dataset
uspto-grants-2011_08
Patent number
US07989451B2

Reaction notes

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