Hydrogen Peroxide → HCID 178438085, compound

HRID 1160640Notes

Reaction equation

HRID 1160640 reaction equation
OO.FC(F)(F)C(OC(=O)C(F)(F)F)=[O:6].[CH2:16]([C:18]1[N:19]=[N+:20]([O-:38])[C:21]2[CH:27]=[CH:26][C:25]([O:28][CH2:29][CH2:30][CH2:31][N:32]3[CH2:37][CH2:36][O:35][CH2:34][CH2:33]3)=[CH:24][C:22]=2[N:23]=1)[CH3:17].FC(F)(F)C(O)=O>C(Cl)Cl.C(Cl)(Cl)Cl.N>[CH2:16]([C:18]1[N:19]=[N+:20]([O-:38])[C:21]2[CH:27]=[CH:26][C:25]([O:28][CH2:29][CH2:30][CH2:31][N:32]3[CH2:33][CH2:34][O:35][CH2:36][CH2:37]3)=[CH:24][C:22]=2[N+:23]=1[O-:6])[CH3:17]

Participants

8

Reactant 4

HCID 784Hydrogen PeroxideHCID 6422Trifluoroacetic acidHCID 9845Trifluoroacetic anhydrideHCID 160813093-Ethyl-6-[3-(4-morpholinyl)propoxy]-1,2,4-benzotriazine 1-Oxide

Product 1

HCID 178438085HCID 178438085, compoundYield 32%

Reagents, catalysts & solvents 3

HCID 222AmmoniaSolventHCID 6212ChloroformSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
20 °C

Procedure

Hydrogen peroxide (70%; 0.53 mL, ca. 10.43 mmol) was added dropwise to a stirred solution of trifluoroacetic anhydride (1.45 mL, 10.43 mmol) in DCM (20 mL) at 5° C. The solution was stirred at 20° C. for 10 min, then cooled to 5° C., added to a solution of 1-oxide 31 (260 mg, 1.04 mmol) and trifluoroactic acid (0.17 mL, 2.23 mmol) in CHCl3 (20 mL) at 5° C. The solution was stirred at 20° C. for 24 h, diluted with dilute aqueous NH3 solution (50 mL) and extracted with CHCl3 (4×50 mL). The combined organic fraction was dried and the solvent evaporated. The residue was purified by column chromatography, eluting with 5% MeOH/DCM to give 1,4-dioxide 32 (90 mg, 32%) as a bright yellow solid, mp 123-126° C.; 1H NMR δ 8.36 (d, J=9.5 Hz, 1 H, H-8), 7.77 (d, J=2.6 Hz, 1 H, H-5), 7.36 (dd, J=9.5, 2.6 Hz, 1 H, H-7), 4.29 (t, J=6.4 Hz, 2 H, CH2), 3.72 (t, J=4.6 Hz, 4 H, 2×CH2O), 3.21 (q, J=7.5 Hz, 2 H, CH2), 2.54 (t, J=7.0 Hz, 2 H, CH2), 2.47 (t, J=4.6 Hz, 4 H, 2×CH2N), 2.10-2.04 (m, 2 H, CH2), 1.44 (t, J=7.5 Hz, 3 H, CH3); 13C NMR δ 165.1, 157.1, 141.5, 129.6, 124.4, 123.4, 98.0, 68.1, 66.9 (2), 55.0, 53.7 (2), 25.9, 24.1, 9.3. Anal. Calcd for C16H22N4O4: C, 57.5; H, 6.3; N, 16.8. Found: C, 57.2; H, 6.5; N, 16.5%.

Workup

  1. temperaturecooled to 5° C.
  2. stirringThe solution was stirred at 20° C. for 24 h
  3. extractionextracted with CHCl3 (4×50 mL)
  4. customThe combined organic fraction was dried
  5. customthe solvent evaporated
  6. customThe residue was purified by column chromatography
  7. washeluting with 5% MeOH/DCM

Sources & evidence

ORD record
ord-9a150a734701449abb74aaf22fd04b67
Source dataset
uspto-grants-2010_10
Patent number
US07816521B2

Reaction notes

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