Dimethylformamide dimethyl acetal → Methyl 5-methoxy-4-oxo-1-(2,2,3,3,7-pentafluoro-2,3-dihydro-1,4-benzodioxin-6-yl)-1,4-dihydropyridazine-3-carboxylate

HRID 1624645Notes

Reaction equation

HRID 1624645 reaction equation
[CH3:1][O:2][CH2:3][C:4](=[O:27])[C:5](=[N:10][NH:11][C:12]1[C:25]([F:26])=[CH:24][C:15]2[O:16][C:17]([F:23])([F:22])[C:18]([F:21])([F:20])[O:19][C:14]=2[CH:13]=1)[C:6]([O:8][CH3:9])=[O:7].[CH3:28]OC(OC)N(C)C>>[CH3:1][O:2][C:3]1[C:4](=[O:27])[C:5]([C:6]([O:8][CH3:9])=[O:7])=[N:10][N:11]([C:12]2[C:25]([F:26])=[CH:24][C:15]3[O:16][C:17]([F:23])([F:22])[C:18]([F:21])([F:20])[O:19][C:14]=3[CH:13]=2)[CH:28]=1

Participants

3

Reactant 2

HCID 78373Dimethylformamide dimethyl acetalHCID 178496271HCID 178496271, compound

Product 1

HCID 59436286Methyl 5-methoxy-4-oxo-1-(2,2,3,3,7-pentafluoro-2,3-dihydro-1,4-benzodioxin-6-yl)-1,4-dihydropyridazine-3-carboxylateYield 37%

Procedure

A mixture of methyl 4-methoxy-3-oxo-2-[(2,2,3,3,7-pentafluoro-2,3-dihydro-1,4-benzodioxin-6-yl)hydrazono]butanoate (6.84 g, 17.2 mmol) in N,N-dimethylformamide dimethyl acetal (68 mL) was heated to reflux for 2.5 h. The mixture was concentrated in vacuo, diluted with brine, extracted with EtOAc, dried over MgSO4, filtered, concentrated in vacuo and purified by column chromatography on silica gel (hexane/EtOAc=50/50 to 0/100 and EtOAc/MeOH=100/0 to 70/30) and on basic silica gel (hexane/EtOAc=80/20 to 0/100 and EtOAc/MeOH=100/0 to 70/30) to yield the title compound (2.58 g, 37% yield) as a pale yellow solid: 1H NMR (DMSO-d6, 300 MHz): δ ppm 3.79 (3H, s), 3.83 (3H, s), 8.01 (1H, d, J=10.2 Hz), 8.16 (1H, d, J=7.2 Hz), 8.58 (1H, s).

Workup

  1. temperaturewas heated
  2. temperatureto reflux for 2.5 h
  3. concentrationThe mixture was concentrated in vacuo
  4. additiondiluted with brine
  5. extractionextracted with EtOAc
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. custompurified by column chromatography on silica gel (hexane/EtOAc=50/50 to 0/100 and EtOAc/MeOH=100/0 to 70/30) and on basic silica gel (hexane/EtOAc=80/20 to 0/100 and EtOAc/MeOH=100/0 to 70/30)

Sources & evidence

ORD record
ord-b5c7a813751d4e60a2abd5b136ef772e
Source dataset
uspto-grants-2014_07
Patent number
US08778944B2

Reaction notes

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