Acetic Anhydride → (Z)-1,1'-(4-(methoxymethylene)-3-oxo-3,4-dihydrocinnoline-1,2-diyl)diethanone

HRID 2236574Notes

Reaction equation

HRID 2236574 reaction equation
[C:1]([N:4]1[C:13]2[C:8](=[CH:9][CH:10]=[CH:11][CH:12]=2)[CH2:7][C:6](=[O:14])[N:5]1[C:15](=[O:17])[CH3:16])(=[O:3])[CH3:2].[C:18]([O:21][C:22](=O)C)(=O)C.COC(OC)OC>CN(C)C=O>[CH3:18][O:21]/[CH:22]=[C:7]1\[C:6](=[O:14])[N:5]([C:15](=[O:17])[CH3:16])[N:4]([C:1](=[O:3])[CH3:2])[C:13]2[C:8]\1=[CH:9][CH:10]=[CH:11][CH:12]=2

Participants

5

Reactant 3

HCID 7918Acetic AnhydrideHCID 9005Trimethyl orthoformateHCID 218292321,2-diacetyl-1,4-dihydro-3(2H)cinnolinone

Product 1

HCID 59300145(Z)-1,1'-(4-(methoxymethylene)-3-oxo-3,4-dihydrocinnoline-1,2-diyl)diethanone

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of 1,2-diacetyl-1,4-dihydro-3(2H)cinnolinone (0.34 g, 1.5 mmol) in dimethylformamide (3.6 mL) is added acetic anhydride (5 mL), followed by trimethylorthoformate (0.64 mL). The mixture is heated at reflux for 12 hours. After cooling to room temperature, the mixture is purified by semi-preparative reverse-phase HPLC, employing a gradient elution from 5% acetonitrile in water with 0.1% trifluoroacetic acid to 100% acetonitrile over 60 minutes. The desired fractions were concentrated under reduced pressure to afford 0.18 g of (Z)-1,1′-(4-(methoxymethylene)-3-oxo-3,4-dihydrocinnoline-1,2-diyl)diethanone.

Workup

  1. temperatureThe mixture is heated
  2. temperatureat reflux for 12 hours
  3. customthe mixture is purified by semi-preparative reverse-phase HPLC
  4. washa gradient elution from 5% acetonitrile in water with 0.1% trifluoroacetic acid to 100% acetonitrile over 60 minutes
  5. concentrationThe desired fractions were concentrated under reduced pressure

Sources & evidence

ORD record
ord-87dadd7f3fac4fceb58d7727d56f23d1
Source dataset
uspto-grants-2010_05
Patent number
US07713994B2

Reaction notes

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