Methylene blue cation → 3H-Phenothiazin-3-one, 7-(dimethylamino)-

HRID 512101Notes

Reaction equation

HRID 512101 reaction equation
[CH3:1][N:2]([C:4]1[CH:5]=[CH:6][C:7]2[N:20]=[C:19]3[C:11](=[CH:12][C:13]([CH:17]=[CH:18]3)=[N+](C)C)[S:10][C:8]=2[CH:9]=1)[CH3:3].CC[O:23]C(C)=O.CO>O.[NH4+].[OH-].[N+]([O-])([O-])=O.[Ag+]>[CH3:1][N:2]([CH3:3])[C:4]1[CH:9]=[C:8]2[C:7](=[CH:6][CH:5]=1)[N:20]=[C:19]1[C:11](=[CH:12][C:13](=[O:23])[CH:17]=[CH:18]1)[S:10]2

Participants

6

Reactant 2

HCID 4139Methylene blue cationHCID 21584119Ethylacetate methanol

Product 1

HCID 730243H-Phenothiazin-3-one, 7-(dimethylamino)-

Reagents, catalysts & solvents 3

HCID 24470Silver NitrateCatalystHCID 962WaterSolventHCID 14923Ammonium HydroxideSolvent

Procedure

To a solution of 0.5 g (1.56 mmol) of Methylene blue in 50 mL of water was added 0.53 g (3.12 mmol) of AgNO3 dissolved in excess NH4OH. The reaction mixture was heated to reflux for an hour, filtered and extracted with EtOAc (20×5 mL). The organic layer was washed with brine, dried over anhydrous Na2SO4, concentrated under diminished pressure. The dark solid was purified on a silica gel column. Elution with 9:1 EtOAc/MeOH gave CPD-18 as a dark solid: yield-25 mg (6%); silica gel TLC Rf 0.27 (9:1 EtOAc/MeOH); 1H NMR (CDCl3) δ 3.16 (s, 1H), 6.60 (d, 1H, J=2.8 Hz), 6.69 (d, 1H, J=2.4 Hz), 6.83 (d, 1H, J=2 Hz), 6.86 (d, 1H, J=2.8 Hz), 7.67 (d, 1H, J=10 Hz), 7.71 (d, 1H, J=9.2 Hz); mass spectrum (MALDI-TOF), m/z 257.07 (M+H)+.

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureto reflux for an hour
  3. filtrationfiltered
  4. extractionextracted with EtOAc (20×5 mL)
  5. washThe organic layer was washed with brine
  6. dry with materialdried over anhydrous Na2SO4
  7. concentrationconcentrated under diminished pressure
  8. customThe dark solid was purified on a silica gel column
  9. washElution with 9:1 EtOAc/MeOH
  10. customgave CPD-18 as a dark solid

Sources & evidence

ORD record
ord-34c97e5a4d0540a798d3adcc18a58676
Source dataset
uspto-grants-2015_08
Patent number
US09102626B2

Reaction notes

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