Hydrogen Peroxide → HCID 135899491, compound

HRID 1669182Notes

Reaction equation

OO.[CH2:3]([N:5]1[CH2:13][C:12]2[C:7](=[CH:8][C:9]3[N+:17]([O-:18])=[N:16][C:15]([NH2:19])=[N:14][C:10]=3[CH:11]=2)[CH2:6]1)[CH3:4].C(O)(C(F)(F)F)=[O:21].O>N>[CH2:3]([N:5]1[CH2:13][C:12]2[C:7](=[CH:8][C:9]3[N+:17]([O-:18])=[N:16][C:15]([NH2:19])=[N+:14]([O-:21])[C:10]=3[CH:11]=2)[CH2:6]1)[CH3:4]

Participants

Conditions

Temperature: 20 °C

Procedure

H2O2 (70%, 0.50 mL, ca. 10 mmol) was added dropwise to a stirred mixture of 1-oxide 249 (328 mg, 1.4 mmol), TFA (4 mL) and water (0.3 mL) at 0° C. and the mixture was stirred at 20° C. Two more aliquots of H2O2 (70%, 0.50 mL, ca. 10 mmol) were added at 3 h and 20 h. After 28 h at 20° C., the mixture was diluted with aqueous NH3 solution (20 mL) and extracted with DCM (5×50 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 250 (68 mg, 19%) as a red solid which was crystallised as the hydrochloride salt: mp (MeOH/DCM) 230° C.; 1H NMR [(CD3)2SO] δ 11.84 (br s, 1H, HCl), 8.27 (s, 1H, H-9), 8.20 (s, 1H, H-5), 8.14 (br s, 2H, NH2), 4.88-5.05 (m, 2H, CH2N), 4.50-4.73 (m, 2H, CH2N), 3.42 (q, J=7.2 Hz, 2H, CH2N), 1.32 (t, J=7.2 Hz, 3H, CH3); 13C NMR [(CD3)2SO] δ 151.4, 143.0, 138.5, 134.0, 130.6, 115.6, 111.4, 56.5, 56.1, 49.1, 10.3; HRMS (FAB+) calcd for C11H14N5O2 (MH+) m/z 248.1148, found 248.1154.

Workup

extractionextracted with DCM (5×50 mL)
customThe combined organic fraction was dried
customthe solvent evaporated
customThe residue was purified by chromatography
washeluting with a gradient (0-10%) of MeOH/DCM

Sources & evidence

ORD record: ord-5125a4b231694463a760fbf1004b0df5
Source dataset: uspto-grants-2011_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07989451B2

Reaction notes

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