Hydrochloric Acid → 6-Methyl-5-nitro-1H-isochromen-1-one

HRID 418471Notes

Reaction equation

HRID 418471 reaction equation
[CH3:1]C(C)([O-])C.[K+].CN(C)C=O.[N+:12]([C:15]1[CH:24]=[CH:23][CH:22]=[C:21]2[C:16]=1[CH:17]=[CH:18][O:19][C:20]2=[O:25])([O-:14])=[O:13].FC(F)(F)C(O)=O.C(=O)([O-])[O-].[K+].[K+].Cl>O.C(O)(=O)C>[CH3:1][C:24]1[C:15]([N+:12]([O-:14])=[O:13])=[C:16]2[C:21](=[CH:22][CH:23]=1)[C:20](=[O:25])[O:19][CH:18]=[CH:17]2

Participants

9

Reactant 6

HCID 313Hydrochloric AcidHCID 6228Dimethylformamide3×HCID 6422Trifluoroacetic acidHCID 11430Potassium CarbonateHCID 100127605-nitro-1H-isochromen-1-oneHCID 23665647Potassium tert-butoxide

Product 1

HCID 595157846-Methyl-5-nitro-1H-isochromen-1-one

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 962WaterSolvent

Procedure

Alternatively, to a solution of potassium tert-butoxide (8.72 g, 0.0777 mol) in N,N-dimethylformamide (250 mL, 3.2 mol) was added a mixture of acetic acid, chloro-, 1,1-dimethylethyl ester (4.335 g, 0.02878 mol) and 5-nitro-1H-isochromen-1-one (5.0 g, 0.026 mol) in N,N-dimethylformamide (50 mL, 0.6 mol) at −20° C. After 1 h, the reaction was poured onto hydrochloric acid (16 mL) and water (35 mL). The aqueous solution was extracted with dichloromethane, washed with brine, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was treated with trifluoroacetic acid (35 mL, 0.45 mol ) for 0.5 h and was removed under reduced pressure. The residue was stirred with potassium carbonate (6.98 g, 0.0505 mol) in N,N-dimethylformamide (200 mL, 2 mol) at 50° C. for 1 h. The reaction was cooled and added with 1 N hydrochloric acid (262 mL), extracted with dichloromethane (80 mL×3), washed with brine and dried over magnesium sulfate. The solvents were removed under reduced pressure and the mixture was purified by flash chromatography to afford the title compound as a yellow solid.

Workup

  1. extractionThe aqueous solution was extracted with dichloromethane
  2. washwashed with brine
  3. dry with materialdried over magnesium sulfate
  4. concentrationconcentrated under reduced pressure
  5. customwas removed under reduced pressure
  6. temperatureThe reaction was cooled
  7. extractionextracted with dichloromethane (80 mL×3)
  8. washwashed with brine
  9. dry with materialdried over magnesium sulfate
  10. customThe solvents were removed under reduced pressure
  11. customthe mixture was purified by flash chromatography

Sources & evidence

ORD record
ord-070efa343b4443e4816cbc01074b01b0
Source dataset
uspto-grants-2012_01
Patent number
US08093265B2

Reaction notes

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