Hydrogen Peroxide → HCID 135481141, compound

Temperature

5 °C

Hydrogen peroxide (70%, 1.1 mL, ca. 22.9 mmol) was added dropwise to a stirred solution of trifluoroacetic anhydride (3.2 mL, 22.9 mmol) in DCM (20 mL) at 5° C. The mixture was stirred at 5° C. for 5 min, warmed to 20° C., stirred for 10 min, and cooled to 5° C. The mixture was added to a stirred solution of 1-oxide 2 (566 mg, 2.3 mmol) and trifluoroacetic acid (353 μL, 4.6 mmol) in CHCl3 (20 mL) at 5° C. and the mixture stirred at 20° C. for 16 h. The solution was carefully diluted with dilute aqueous NH3 solution (20 mL) and the mixture extracted with CHCl3 (5×50 mL). The 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 3 (207 mg, 34%) as a red solid, mp (MeOH/EtOAc) 187-189° C.; 1H NMR δ 8.19 (d, J=9.0 Hz, 1 H, H-8), 8.05 (d, J=1.7 Hz, 1 H, H-5), 7.44. (br s, 1 H, NH), 7.29 (dd, J=9.0, 1.7 Hz, 1 H, H-7), 3.58-3.64 (m, 2 H, CH2N), 2.57-2.61 (m, 2 H, CH2N), 2.56 (s, 3 H, CH3), 2.28 [s, 6 H, (CH3)2]; 13C NMR δ 149.9, 148.0, 138.2, 129.3, 128.8, 121.4, 116.0, 57.4, 45.2 (2), 38.8, 22.3. Anal. Calcd for C12H17N5O2: C, 54.7; H, 6.5; N, 26.6. Found: C, 54.3: H, 6.7; N, 26.8%.

1. temperaturewarmed to 20° C.
2. stirringstirred for 10 min
3. temperaturecooled to 5° C
4. stirringthe mixture stirred at 20° C. for 16 h
5. extractionthe mixture extracted with CHCl3 (5×50 mL)
6. customThe organic fraction was dried
7. customthe solvent evaporated
8. customThe residue was purified by chromatography
9. washeluting with a gradient (0-10%) of MeOH/DCM

ORD record

ord-7a42432d70c048389446c250ec5243fe

Source dataset

uspto-grants-2010_10

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07816521B2