Hydrogen Peroxide → HCID 178438081, compound

HRID 1669115Notes

Reaction equation

HRID 1669115 reaction equation
OO.[CH2:3]([C:5]1[N:6]=[N+:7]([O-:25])[C:8]2[CH:17]=[C:16]3[C:12]([CH2:13][CH:14]([CH2:18][N:19]4[CH2:24][CH2:23][O:22][CH2:21][CH2:20]4)[CH2:15]3)=[CH:11][C:9]=2[N:10]=1)[CH3:4].C(OC(C(F)(F)F)=O)(C(F)(F)F)=[O:27].C(O)(C(F)(F)F)=O.C([O-])([O-])=O.[Na+].[Na+]>C(Cl)Cl>[CH2:3]([C:5]1[N:6]=[N+:7]([O-:25])[C:8]2[CH:17]=[C:16]3[C:12]([CH2:13][CH:14]([CH2:18][N:19]4[CH2:20][CH2:21][O:22][CH2:23][CH2:24]4)[CH2:15]3)=[CH:11][C:9]=2[N+:10]=1[O-:27])[CH3:4]

Participants

7

Reactant 5

HCID 784Hydrogen PeroxideHCID 6422Trifluoroacetic acidHCID 9845Trifluoroacetic anhydrideHCID 10340Sodium CarbonateHCID 25140026HCID 25140026, compound

Product 1

HCID 178438081HCID 178438081, compoundYield 21%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
20 °C

Procedure

H2O2 (70%, 0.95 mL, ca 16 mmol) was added drop-wise (over 10 min) to a stirred solution of 1-oxide 143 (503 mg, 1.6 mmol), TFAA (2.56 mL, 16.0 mmol) and TFA (0.66 mL, 8.0 mmol) in DCM (60 mL) at 20° C. and the mixture was stirred at 20° C. for 7 h. Dilute Na2CO3 solution (40 mL) was added and the mixture was extracted with DCM (5×80 mL). The combined organic fraction was dried and the solvent evaporated to give an oil which was purified by chromatography, eluting with a gradient (0-2%) of MeOH/DCM, to give 1,4-dioxide 144 (87 mg, 21%) as a yellow solid: mp (MeOH/DCM) 164-165° C.; 1H NMR δ 8.31 (s, 1H, H-9), 8.25 (s, 1H, H-5), 3.72 (t, J=4.6 Hz, 4H, 2×CH2O), 3.17-3.34 (m, 4H, CH2), 2.80-2.95 (m, 3H, CH2, H-7), 2.45 (t, J=4.6 Hz, 4H, 2×CH2N), 2.38 (d, J=7.7 Hz, 2H, CH2), 1.43 (t, J=7.5 Hz, 3H, CH3); 13C NMR δ 155.7, 154.1, 149.5, 139.2, 134.0, 116.3, 114.3, 67.0 (2), 63.1, 53.9 (2), 37.7, 37.2, 36.6, 23.8, 9.2. Anal. calcd for C17H22N4O3: C, 61.8; H, 6.7; N, 17.0. Found: C, 62.1; H, 6.7; N, 16.8%.

Workup

  1. extractionthe mixture was extracted with DCM (5×80 mL)
  2. customThe combined organic fraction was dried
  3. customthe solvent evaporated
  4. customto give an oil which
  5. customwas purified by chromatography
  6. washeluting with a gradient (0-2%) of MeOH/DCM

Sources & evidence

ORD record
ord-e50bb0e5a9b349359261ce70afbf1e61
Source dataset
uspto-grants-2011_08
Patent number
US07989451B2

Reaction notes

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