Hydrogen Peroxide → HCID 135526555, compound

HRID 1669044Notes

Reaction equation

HRID 1669044 reaction equation
OO.[CH3:3][O:4][CH:5]1[CH2:8][N:7]([CH2:9][CH2:10][CH2:11][NH:12][C:13]2[N:14]=[N+:15]([O-:26])[C:16]3[CH:25]=[C:24]4[C:20]([CH2:21][CH2:22][CH2:23]4)=[CH:19][C:17]=3[N:18]=2)[CH2:6]1.C(O)(C(F)(F)F)=[O:28]>C(Cl)Cl.N>[CH3:3][O:4][CH:5]1[CH2:8][N:7]([CH2:9][CH2:10][CH2:11][NH:12][C:13]2[N:14]=[N+:15]([O-:26])[C:16]3[CH:25]=[C:24]4[C:20]([CH2:21][CH2:22][CH2:23]4)=[CH:19][C:17]=3[N+:18]=2[O-:28])[CH2:6]1

Participants

6

Reactant 3

HCID 784Hydrogen PeroxideHCID 6422Trifluoroacetic acidHCID 11951462HCID 11951462, compound

Product 1

HCID 135526555HCID 135526555, compoundYield 30%

Reagents, catalysts & solvents 2

HCID 222AmmoniaSolventHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
20 °C

Procedure

H2O2 (70%, 2.0 mL, ca. 40 mmol) was added dropwise to a stirred solution of TFM (5.6 mL, 40 mmol) in DCM (50 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 54 (1.3 g, 4.0 mmol) and TFA (1.5 mL, 20 mmol) in DCM (50 mL) at 0° C. The solution was stirred at 20° C. for 26 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 (0-15%) of MeOH/DCM, to give 1,4-dioxide 55 (400 mg, 30%) as a red solid: mp 150-152° C.; 1H NMR δ 8.12 (s, 1H, H-9), 8.10 (s, 1H, H-5), 8.06 (br s, 1H, NH), 4.18 (p, J=5.9 Hz, 1H, CHO), 3.91 (br s, 2H, CH2N), 3.64 (t, J=6.4 Hz, 2H, CH2N), 3.28 (s, 3H, OCH3), 2.98-3.13 (m, 6H, H-6, H-8, CH2N), 2.80 (t, J=6.3 Hz, 2H, CH2N), 2.20 (p, J=7.5 Hz, 2H, H-7), 1.82 (p, J=6.4 Hz, 2H, CH2); 13C NMR δ 155.7, 149.4, 145.7, 138.0, 129.7, 115.8, 111.6, 69.3, 61.4 (2), 57.3, 56.2, 40.4, 33.4, 32.4, 26.0, 25.6; MS (APCI) m/z 346 (MH+, 100%); HRMS (FAB+) calcd for C17H24N5O3 (MH+) m/z 346.1879, found 346.1878.

Workup

  1. temperaturecooled to 0° C.
  2. stirringThe solution was stirred at 20° C. for 26 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 (0-15%) of MeOH/DCM

Sources & evidence

ORD record
ord-a245218a7b1549128e22ebdb7185c836
Source dataset
uspto-grants-2011_08
Patent number
US07989451B2

Reaction notes

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