Hydrogen Peroxide → HCID 178438084, compound

HRID 1669189Notes

Reaction equation

HRID 1669189 reaction equation
OO.C(OC(C(F)(F)F)=O)(C(F)(F)F)=[O:4].[CH2:16]([C:18]1[N:19]=[N+:20]([O-:33])[C:21]2[C:30]([N:31]=1)=[CH:29][C:28]1[CH2:27][N:26]([CH3:32])[CH2:25][CH2:24][C:23]=1[CH:22]=2)[CH3:17].C(O)(C(F)(F)F)=O>C(Cl)Cl.N>[CH2:16]([C:18]1[N:19]=[N+:20]([O-:33])[C:21]2[C:30]([N+:31]=1[O-:4])=[CH:29][C:28]1[CH2:27][N:26]([CH3:32])[CH2:25][CH2:24][C:23]=1[CH:22]=2)[CH3:17]

Participants

7

Reactant 4

HCID 784Hydrogen PeroxideHCID 6422Trifluoroacetic acidHCID 9845Trifluoroacetic anhydrideHCID 25140184HCID 25140184, compound

Product 1

HCID 178438084HCID 178438084, compoundYield 17.1%

Reagents, catalysts & solvents 2

HCID 222AmmoniaSolventHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
20 °C

Procedure

H2O2 (70%, 2.4 mL, ca. 25 mmol) was added dropwise to a stirred solution of TFAA (3.5 mL, 25 mmol) in DCM (20 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 260 (590 mg, 2.4 mmol) and TFA (0.96 mL, 12.2 mmol) in DCM (20 mL) at 0° C. The solution was stirred at 20° C. for 4 h, diluted with dilute aqueous NH3 solution (80 mL) and extracted with DCM (4×150 mL). The combined organic fraction was dried and the solvent evaporated. The residue was purified by chromatography, eluting with a gradient (2-5%) of MeOH/DCM, to give 1,4-dioxide 261 (107 mg, 17%) as a yellow solid: mp 124-128° C.; 1H NMR δ 8.23 (s, 1H, H-10), 8.18 (s, 1H, H-5), 3.83 (s, 2H, H-6), 3.15-3.24 (m, 4H, CH2, H-8), 2.78 (t, J=6.0 Hz, 2H, H-9), 2.51 (s, 3H, NCH3), 1.43 (t, J=7.5 Hz, 3H, CH3); 13C NMR δ 149.3, 145.5, 136.5, 135.3, 129.3, 120.5, 116.3, 58.1, 51.9, 45.8, 29.6, 23.9, 9.3; MS (APCI) m/z 261 (MH+, 100%). Anal. calcd for C13H16N4O2.¼CH2Cl2: C, 56.5; H, 5.9; N, 19.9. Found: C, 56.6; H, 5.9; N, 19.7%.

Workup

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

Sources & evidence

ORD record
ord-06a23c5e59cc4a6e9333c6fd6d44cc4d
Source dataset
uspto-grants-2011_08
Patent number
US07989451B2

Reaction notes

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