Hydrogen Peroxide → HCID 178495918, compound

HRID 1669070Notes

Reaction equation

HRID 1669070 reaction equation
OO.[CH3:3][O:4][CH2:5][CH2:6][N:7]([CH2:25][CH2:26][O:27][CH3:28])[CH2:8][CH2:9][CH2:10][C:11]1[N:12]=[N+:13]([O-:24])[C:14]2[CH:23]=[C:22]3[C:18]([CH2:19][CH2:20][CH2:21]3)=[CH:17][C:15]=2[N:16]=1.C(O)(C(F)(F)F)=[O:30]>C(Cl)Cl.N>[O-:24][N+:13]1[C:14]2[CH:23]=[C:22]3[C:18](=[CH:17][C:15]=2[N+:16]([O-:30])=[C:11]([CH2:10][CH2:9][CH2:8][N:7]([CH2:25][CH2:26][O:27][CH3:28])[CH2:6][CH2:5][O:4][CH3:3])[N:12]=1)[CH2:19][CH2:20][CH2:21]3

Participants

6

Reactant 3

HCID 784Hydrogen PeroxideHCID 6422Trifluoroacetic acidHCID 11951825HCID 11951825, compound

Product 1

HCID 178495918HCID 178495918, compoundYield 72.6%

Reagents, catalysts & solvents 2

HCID 222AmmoniaSolventHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

H2O2 (70%, 2.0 mL, 39 mmol) was added dropwise to a stirred solution of TFM (5.4 mL, 39 mmol) in DCM (50 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 80 (1.50 g, 4.2 mmol) and TFA (1.5 mL, 1.95 mmol) in DCM (50 mL) at 0° C. The solution was stirred at 20° C. for 6 h, diluted with dilute aqueous NH3 solution (36 mL) and extracted with DCM (3×150 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 81 (533 mg, 35%) as a red gum: 1H NMR δ 8.28 (s, 1H, H-9), 8.24 (s, 1H, H-5), 3.78 (br t, J=4.7 Hz, 4H, 2×CH2O), 3.40-3.45 (m, 6H, 3×CH2), 3.33 [s, 6H, 2×OCH3), 3.19-3.23 (m, 2H, CH2), 3.12-3.17 (m, 4H, H-6, H-8), 2.34-2.38 (m, 2H, CH2), 2.22-2.28 (m, 2H, H-7); 13C NMR δ 155.5, 152.5, 151.1, 139.0, 134.0, 115.8, 113.8, 67.2 (2), 58.9 (2), 52.9 (3), 33.4, 32.9, 27.2, 25.5, 18.8; HRMS (FAB+) calcd for C19H29N4O4 (MH+) m/z 377.2189, found 377.2185.

Workup

  1. temperaturewarmed to 20° C. for 10 min
  2. temperaturecooled to 0° C.
  3. stirringThe solution was stirred at 20° C. for 6 h
  4. extractionextracted with DCM (3×150 mL)
  5. customThe combined organic fraction was dried
  6. customthe solvent evaporated
  7. customThe residue was purified by chromatography
  8. washeluting with a gradient (0-10%) of MeOH/DCM

Sources & evidence

ORD record
ord-9c6acf239cc14989982af574d2423e63
Source dataset
uspto-grants-2011_08
Patent number
US07989451B2

Reaction notes

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