Hydrogen Peroxide → HCID 135899476, compound

HRID 1669155Notes

Reaction equation

HRID 1669155 reaction equation
OO.C(OC(C(F)(F)F)=O)(C(F)(F)F)=[O:4].[CH2:16]([N:18]([CH2:36][CH3:37])[CH2:19][CH2:20][NH:21][C:22]1[N:23]=[N+:24]([O-:35])[C:25]2[CH:31]=[C:30]3[CH2:32][CH2:33][O:34][C:29]3=[CH:28][C:26]=2[N:27]=1)[CH3:17].C(O)(C(F)(F)F)=O>C(Cl)Cl.C(Cl)(Cl)Cl.N>[O-:35][N+:24]1[C:25]2[CH:31]=[C:30]3[CH2:32][CH2:33][O:34][C:29]3=[CH:28][C:26]=2[N+:27]([O-:4])=[C:22]([NH:21][CH2:20][CH2:19][N:18]([CH2:16][CH3:17])[CH2:36][CH3:37])[N:23]=1

Participants

8

Reactant 4

HCID 784Hydrogen PeroxideHCID 6422Trifluoroacetic acidHCID 9845Trifluoroacetic anhydrideHCID 25139755HCID 25139755, compound

Product 1

HCID 135899476HCID 135899476, compoundYield 38.1%

Reagents, catalysts & solvents 3

HCID 222AmmoniaSolventHCID 6212ChloroformSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
20 °C

Procedure

H2O2 (70%, 0.38 mL, ca. 2.8 mmol) was added dropwise to a stirred solution of TFAA (1.1 mL, 2.8 mmol) in DCM (15 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 209 (235 mg, 0.78 mmol) and TFA (0.13 mL, 1.7 mmol) in CHCl3 (15 mL) at 0° C. The solution was stirred at 20° C. for 4 h, diluted with dilute aqueous NH3 solution until basic and extracted with CHCl3 (3×25 mL). The combined organic fraction was dried and the solvent evaporated. The residue was purified by chromatography, eluting with a gradient (5-10%) of MeOH/DCM, to give 1,4-dioxide 210 (95 mg, 38%) as a red solid: mp 187-190° C.; 1H NMR (CD3OD) δ 8.16 (t, J=1.7 Hz, 1H, H-9), 7.30 (s, 1H, H-5), 4.85 (t, J=8.4 Hz, 2H, H-7), 3.90-3.94 (m, 2H, CH2), 3.40-3.49 (m, 4H, H-8, CH2), 3.36 (q, J=7.3 Hz, 4H, CH2), 1.37 (t, J=7.3 Hz, 6H, CH3), NH not observed; 13C NMR δ 169.8, 151.5, 142.3, 135.5, 128.2, 119.0, 93.7, 75.6, 51.7, 49.0 (2), 37.3, 29.4, 9.1 (2); HRMS (FAB+) calcd for C15H22N5O3 (MH+) m/z 320.1723, found 320.1726.

Workup

  1. temperaturecooled to 0° C.
  2. stirringThe solution was stirred at 20° C. for 4 h
  3. extractionextracted with CHCl3 (3×25 mL)
  4. customThe combined organic fraction was dried
  5. customthe solvent evaporated
  6. customThe residue was purified by chromatography
  7. washeluting with a gradient (5-10%) of MeOH/DCM

Sources & evidence

ORD record
ord-8911787b62084dbaa714c25863a61856
Source dataset
uspto-grants-2011_08
Patent number
US07989451B2

Reaction notes

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