Hydrogen Peroxide → N-(6-nitro-2,3-dihydro-1H-inden-5-yl)acetamide
Reaction equation
OO.C(O[C:10]([C:12](F)(F)F)=[O:11])(C(F)(F)F)=O.C(NC1N=[N+:21]([O-:35])[C:22]2[CH:31]=[C:30]3[C:26]([CH2:27][CH:28](N(C)C)[CH2:29]3)=[CH:25][C:23]=2[N:24]=1)C.C(O)(C(F)(F)F)=[O:37]>C(Cl)Cl.N>[N+:21]([C:22]1[CH:31]=[C:30]2[C:26]([CH2:27][CH2:28][CH2:29]2)=[CH:25][C:23]=1[NH:24][C:10](=[O:11])[CH3:12])([O-:35])=[O:37]Participants
Conditions
- Temperature
- 0 °C
Procedure
H2O2 (70%, 0.35 mL, ca. 6.9 mmol) was added dropwise to a stirred solution of TFAA (1.0 mL, 6.9 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 113 (188 mg, 0.7 mmol) and TFA (0.26 mL, 3.4 mmol) in DCM (10 mL) at 0° C. The solution was stirred at 20° C. for 6 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 (0-10%) of MeOH/DCM, to give (i) starting material 113 (175 mg, 93%) and (ii) 1,4-dioxide 114 (8 mg, 4%) as a red gum: 1H NMR δ 8.11 (s, 1H, H-9), 8.08 (s, 1H, H-5), 6.98 (br s, 1H, NH), 3.63 (dq, J=7.2, 1.0 Hz, 2H, CH2N), 3.15-3.30 (m, 3H, CH, CH2), 2.95-3.07 (m, 2H, CH2), 2.33 [s, 6H, N(CH3)2], 1.36 (t, J=7.2 Hz, 3H, CH3); MS (FAB+) m/z 290 (MH+, 20%), 274 (5); HRMS (FAB+) calcd for C14H20N5O2 (MH+) m/z 290.1617, found 290.1607.
Workup
- temperaturewarmed to 20° C. for 10 min
- temperaturecooled to 0° C.
- stirringThe solution was stirred at 20° C. for 6 h
- extractionextracted with CHCl3 (4×30 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-0f6d48c8d8894c0dadfb3a9fcda0a71e
- Source dataset
- uspto-grants-2011_08
- Patent number
- US07989451B2
Reaction notes
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