Acetic Acid → HCID 178438082, compound

HRID 1669108Notes

Reaction equation

HRID 1669108 reaction equation
OO.[Si]([O:10][CH2:11][CH:12]1[CH2:27][C:26]2[C:14](=[CH:15][C:16]3[N+:21]([O-:22])=[N:20][C:19]([CH2:23][CH3:24])=[N:18][C:17]=3[CH:25]=2)[CH2:13]1)(C(C)(C)C)(C)C.CC(O)=[O:30].O>CO.CCN(CC)CC>[CH2:23]([C:19]1[N:20]=[N+:21]([O-:22])[C:16]2[CH:15]=[C:14]3[C:26]([CH2:27][CH:12]([CH2:11][OH:10])[CH2:13]3)=[CH:25][C:17]=2[N+:18]=1[O-:30])[CH3:24]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 784Hydrogen PeroxideHCID 962WaterHCID 25139185HCID 25139185, compound

Product 1

HCID 178438082HCID 178438082, compoundYield 18%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 8471TriethylamineSolvent

Conditions

Temperature
80 °C

Procedure

H2O2 (70%, 1.5 mL, ca. 30.0 mmol) was added dropwise to a stirred solution of 1-oxide 135 (273 mg, 0.76 mmol) and HOAc (6 mL) at 50° C. and the reaction was stirred at 80° C. for 20 h. The mixture was cooled, water (50 mL) was added and the mixture was extracted with DCM (5×50 mL). The combined organic fraction was dried and the solvent evaporated to give a yellow oil which was treated with Et3N (3 mL) in MeOH (20 mL) at 20° C. for 66 h. The solvent was evaporated and the residue was purified by chromatography, eluting with a gradient (0-5%) of MeOH/DCM, to give 1,4-dioxide 136 (35 mg, 18%) as a yellow solid: mp (MeOH/DCM) 157-158° C.; 1H NMR δ 8.31 (s, 1H, H-9), 8.26 (s, 1H, H-5), 3.72 (br d, J=5.8 Hz, 2H, CH2O), 3.25-3.35 (m, 2H, CH2), 3.20 (q, J=7.5 Hz, 2H, CH2), 3.00-3.10 (m, 2H, CH2), 2.81-2.92 (m, 1H, H-7H), 1.43 (t, J=7.5 Hz, 3H, CH3), OH not observed; HRMS calcd for C13H15N3O3 (M+) m/z 261.1113, found 261.1115. Anal. calcd for C13H15N3O3: C, 59.8; H, 5.8; N, 16.1. Found: C, 59.6; H, 5.9; N, 15.9%.

Workup

  1. temperatureThe mixture was cooled
  2. extractionthe mixture was extracted with DCM (5×50 mL)
  3. customThe combined organic fraction was dried
  4. customthe solvent evaporated
  5. customto give a yellow oil which
  6. customThe solvent was evaporated
  7. customthe residue was purified by chromatography
  8. washeluting with a gradient (0-5%) of MeOH/DCM

Sources & evidence

ORD record
ord-3af2bf83e1d9446089cde28cff55de07
Source dataset
uspto-grants-2011_08
Patent number
US07989451B2

Reaction notes

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