Hydrogen Peroxide → HCID 135526547, compound

HRID 1669028Notes

Reaction equation

HRID 1669028 reaction equation
OO.C(OC(C(F)(F)F)=O)(C(F)(F)F)=[O:4].[CH3:16][O:17][CH:18]1[CH2:23][CH2:22][CH2:21][N:20]([CH2:24][CH2:25][NH:26][C:27]2[N:28]=[N+:29]([O-:40])[C:30]3[CH:39]=[C:38]4[C:34]([CH2:35][CH2:36][CH2:37]4)=[CH:33][C:31]=3[N:32]=2)[CH2:19]1.C(O)(C(F)(F)F)=O>C(Cl)Cl.C(Cl)(Cl)Cl.N>[CH3:16][O:17][CH:18]1[CH2:23][CH2:22][CH2:21][N:20]([CH2:24][CH2:25][NH:26][C:27]2[N:28]=[N+:29]([O-:40])[C:30]3[CH:39]=[C:38]4[C:34]([CH2:35][CH2:36][CH2:37]4)=[CH:33][C:31]=3[N+:32]=2[O-:4])[CH2:19]1

Participants

8

Reactant 4

HCID 784Hydrogen PeroxideHCID 6422Trifluoroacetic acidHCID 9845Trifluoroacetic anhydrideHCID 11951115HCID 11951115, compound

Product 1

HCID 135526547HCID 135526547, compoundYield 8.2%

Reagents, catalysts & solvents 3

HCID 222AmmoniaSolventHCID 6212ChloroformSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
20 °C

Procedure

H2O2 (70%, 2.5 mL, ca. 51 mmol) was added dropwise to a stirred solution of TFAA (7.1 mL, 51 mmol) in DCM (70 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 40 (1.75 g, 5.1 mmol) and TFA (0.84 mL, 11 mmol) in CHCl3 (70 mL) at 0° C. The solution was stirred at 20° C. for 5 h, diluted with dilute aqueous NH3 solution until basic and extracted with CHCl3 (3×80 mL). The combined organic fraction was dried and the solvent evaporated. The residue was purified by column chromatography, eluting with a gradient (4-20%) of MeOH/DCM, to give 1,4-dioxide 41 (0.15 g, 8%) as a red gum: 1H NMR δ 8.91 (br s, 1H, NH), 8.05 (s, 2H, H-5, H-9), 4.09 (t, J=5.8 Hz, 2H, CH2N), 3.84 (td, J=12.8, 1.9 Hz, 1H, CHO), 3.57-3.66 (m, 4H, 2×CH2), 3.57 (s, 3H, OMe), 3.40 (td, J=13.3, 3.5 Hz, 1H, CH2), 3.01-3.12 (m, 5H, H-6, H-8, CH2), 2.19 (p, J=7.4 Hz, 2H, H-7), 2.16-2.23 (m, 1H, CH2), 2.02-2.08 (m, 1H, CH2), 1.62-1.72 (m, 1H, CH2), 1.37-1.48 (m, 1H, CH2); 13C NMR δ 155.6, 149.4, 146.1, 138.1, 129.7, 115.5, 111.7, 73.2, 69.7, 67.6, 61.4, 56.9, 36.5, 33.3, 32.4, 28.5, 25.6, 20.3; HRMS (FAB+) calcd for C18H26N5O3 (MH+) m/z 360.2036, found 360.2039.

Workup

  1. temperaturecooled to 0° C.
  2. stirringThe solution was stirred at 20° C. for 5 h
  3. extractionextracted with CHCl3 (3×80 mL)
  4. customThe combined organic fraction was dried
  5. customthe solvent evaporated
  6. customThe residue was purified by column chromatography
  7. washeluting with a gradient (4-20%) of MeOH/DCM

Sources & evidence

ORD record
ord-89ba310f840e4ffe932ded0f6ec59ce3
Source dataset
uspto-grants-2011_08
Patent number
US07989451B2

Reaction notes

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