m-Chloroperbenzoic acid → HCID 71224558, compound

HRID 2402942Notes

Reaction equation

HRID 2402942 reaction equation
[CH3:1][N:2]1[C:7](=[O:8])[C:6]2[CH:9]=[N:10][C:11](SC)=[N:12][C:5]=2[C:4]([CH3:15])=[N:3]1.ClC1C=C(C=CC=1)C(OO)=O.CCN(C(C)C)C(C)C.[CH3:36][N:37]1[CH2:42][CH2:41][N:40]([C:43]2[CH:49]=[CH:48][C:46]([NH2:47])=[CH:45][CH:44]=2)[CH2:39][CH2:38]1>ClCCl>[CH3:1][N:2]1[C:7](=[O:8])[C:6]2[CH:9]=[N:10][C:11]([NH:47][C:46]3[CH:45]=[CH:44][C:43]([N:40]4[CH2:39][CH2:38][N:37]([CH3:36])[CH2:42][CH2:41]4)=[CH:49][CH:48]=3)=[N:12][C:5]=2[C:4]([CH3:15])=[N:3]1

Participants

6

Reactant 4

HCID 70297m-Chloroperbenzoic acidHCID 81531DiisopropylethylamineHCID 7372534-(4-Methylpiperazin-1-yl)anilineHCID 71224662HCID 71224662, compound

Product 1

HCID 71224558HCID 71224558, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
100 °C

Procedure

To a cold (0° C.) solution of Example 1C (100 mg, 0.450 mmol) in dichloromethane (1.5 mL) was added meta-chloroperoxybenzoic acid (122 mg, 0.495 mmol) in a single portion. After 1 hour, the reaction mixture was partitioned between 10% sodium thiosulfate solution and ethyl acetate. The layers were separated, and the organic layer was washed with saturated sodium bicarbonate solution, dried with anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The residue was dissolved in N,N-dimethylformamide (3 mL). Hunig's base (157 μl, 0.900 mmol) and 4-(4-methylpiperazin-1-yl)aniline (86 mg, 0.450 mmol) were added to the solution, and the reaction mixture was heated at 100° C. overnight. The reaction mixture was cooled to room temperature and partitioned between water and ethyl acetate. The organic layer was concentrated under reduced pressure. The crude residue was purified by RP-MPLC (125 g C-18 silica gel), eluting with a gradient of 5 to 50% acetonitrile in water each containing 0.1% TFA, to provide the title compound. MS ESI(+) m/z 366.2 [M+H]+; 1H NMR (300 MHz, DMSO-d6): δ ppm 10.33 (s, 1H), 9.22 (s, 1H), 7.77-7.62 (m, 2H), 6.99-6.91 (m, 2H), 3.63 (s, 3H), 3.20-3.02 (m, 4H), 2.46-2.43 (m, 4H), 2.22 (s, 3H).

Workup

  1. customthe reaction mixture was partitioned between 10% sodium thiosulfate solution and ethyl acetate
  2. customThe layers were separated
  3. washthe organic layer was washed with saturated sodium bicarbonate solution
  4. dry with materialdried with anhydrous sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. dissolutionThe residue was dissolved in N,N-dimethylformamide (3 mL)
  8. temperatureThe reaction mixture was cooled to room temperature
  9. custompartitioned between water and ethyl acetate
  10. concentrationThe organic layer was concentrated under reduced pressure
  11. customThe crude residue was purified by RP-MPLC (125 g C-18 silica gel)
  12. washeluting with a gradient of 5 to 50% acetonitrile in water each containing 0.1% TFA

Sources & evidence

ORD record
ord-2d9d9c1a2bd6432588d0873350b872e2
Source dataset
uspto-grants-2014_08
Patent number
US08796289B2

Reaction notes

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