Hydrogen Peroxide → HCID 135899511, compound

HRID 1669136Notes

Reaction equation

HRID 1669136 reaction equation
OO.C(OC(C(F)(F)F)=O)(C(F)(F)F)=[O:4].[N:16]1([CH2:22][CH2:23][CH2:24][NH:25][C:26]2[N:27]=[N+:28]([O-:40])[C:29]3[CH:39]=[C:38]4[C:33]([CH2:34][CH2:35][CH2:36][CH2:37]4)=[CH:32][C:30]=3[N:31]=2)[CH2:21][CH2:20][O:19][CH2:18][CH2:17]1.C(O)(C(F)(F)F)=O>C(Cl)Cl.N>[N:16]1([CH2:22][CH2:23][CH2:24][NH:25][C:26]2[N:27]=[N+:28]([O-:40])[C:29]3[CH:39]=[C:38]4[C:33]([CH2:34][CH2:35][CH2:36][CH2:37]4)=[CH:32][C:30]=3[N+:31]=2[O-:4])[CH2:21][CH2:20][O:19][CH2:18][CH2:17]1

Participants

7

Reactant 4

HCID 784Hydrogen PeroxideHCID 6422Trifluoroacetic acidHCID 9845Trifluoroacetic anhydrideHCID 25139621HCID 25139621, compound

Product 1

HCID 135899511HCID 135899511, compoundYield 13%

Reagents, catalysts & solvents 2

HCID 222AmmoniaSolventHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

H2O2 (70%, 0.36 mL, ca. 6.0 mmol) was added dropwise to a stirred solution of TFAA (0.96 mL, 6.0 mmol) in DCM (5 mL) at 0° C. The solution was stirred at 0° C. for 5 min, warmed to 20° C. for 10 min, then added to a stirred solution of 1-oxide 179 (204 mg, 0.60 mmol) and TFA (0.24 mL, 3.0 mmol) in DCM (5 mL) at 0° C. The solution was stirred at 20° C. for 8 h, diluted with dilute aqueous NH3 solution (10 mL) and extracted with DCM (5×50 mL). The combined organic fraction was dried and the solvent evaporated. The residue was purified by chromatography, eluting with a gradient (0-2%) of MeOH/DCM, to give 1,4-dioxide 180 (28 mg, 13%) as a red solid which was converted to the hydrochloride salt: mp (MeOH/DCM) 182-185° C.; 1H NMR [(CD3)2SO] δ 10.29 (s, 1H, HCl), 8.35 (br s, 1H, NH), 7.95 (s, 1H, H-10), 7.87 (s, 1H, H-5), 3.92-4.01 (m, 2H, CH2O), 3.37 (m, 4H, CH2N, CH2O), 2.88-3.22 (m, 8H, 2×CH2N, H-6, H-9), 2.53 (t, J=5.6 Hz, 2H, CH2N), 2.00-2.09 (m, 2H, CH2N), 1.74-1.83 (m, 4H, H-7, H-8); 13C NMR [(CD3)2SO] δ 149.2, 147.8, 138.0, 136.1, 128.5, 119.4, 115.0, 63.0 (2), 53.5, 50.9 (2), 37.9, 29.4, 28.5, 22.7, 21.7, 21.6. Anal. calcd for C18H25N5O3.2HCl.2H2O: C, 46.2; H, 6.7; N, 15.0. Found: C, 46.3; H, 6.4; N, 15.0%.

Workup

  1. temperaturewarmed to 20° C. for 10 min
  2. stirringThe solution was stirred at 20° C. for 8 h
  3. extractionextracted with DCM (5×50 mL)
  4. customThe combined organic fraction was dried
  5. customthe solvent evaporated
  6. customThe residue was purified by chromatography
  7. washeluting with a gradient (0-2%) of MeOH/DCM

Sources & evidence

ORD record
ord-b334cfb019664dc8ad36f14e721fad2d
Source dataset
uspto-grants-2011_08
Patent number
US07989451B2

Reaction notes

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