Pivalaldehyde → HCID 12997788, compound

HRID 23521Notes

Reaction equation

HRID 23521 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=O)[C:9]([C:12]2C=C[N:15]=[C:14](F)[CH:13]=2)=[N:10][OH:11])=[CH:4][CH:3]=1.[CH3:20][C:21]([CH3:25])([CH3:24])[CH:22]=O.[C:26]([O-:29])(=O)[CH3:27].[NH4+:30]>C(O)(=O)C>[C:21]([C:22]1[N:10]([OH:11])[C:9]([C:12]2[CH:13]=[CH:14][NH:15][C:26](=[O:29])[CH:27]=2)=[C:8]([C:5]2[CH:6]=[CH:7][C:2]([F:1])=[CH:3][CH:4]=2)[N:30]=1)([CH3:25])([CH3:24])[CH3:20]

Participants

5

Reactant 3

HCID 12417PivalaldehydeHCID 517165Ammonium AcetateHCID 1363357801-(2-Fluoropyridin-4-yl)-2-(4-fluorophenyl)ethane-1,2-dione-1-oxime

Product 1

HCID 12997788HCID 12997788, compound

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

To a solution of 1-(4-fluorophenyl)-2-(2-fluoropyridin-4-yl)ethane-1,2-dione 2-oxime (47.3 g, 0.18 mol) in acetic acid (1 L) under nitrogen was added trimethylacetaldehyde (21.6 mL, 0.19 mol) followed by ammonium acetate (277.5 g, 3.6 mol) and then it was heated to reflux for three hours. The acetic acid was removed under reduced pressure and the remaining material was taken up in water. The pH of the solution was adjusted to 8-10 by addition of solid ammonium hydroxide and was extracted with EtOAc. The solvent was removed under reduced pressure and the crude product was dissolved in methanol with sufficient ethanol added to effect dissolution. The solvent was removed under reduced pressure; the product was twice dissolved in ethanol and concentrated to a small volume under reduced pressure to azeotropically remove water. The title compound was recrystallized from ethanol and hexane (28.8 g).

Workup

  1. temperatureit was heated
  2. temperatureto reflux for three hours
  3. customThe acetic acid was removed under reduced pressure
  4. additionThe pH of the solution was adjusted to 8-10 by addition of solid ammonium hydroxide
  5. extractionwas extracted with EtOAc
  6. customThe solvent was removed under reduced pressure
  7. dissolutionthe crude product was dissolved in methanol with sufficient ethanol
  8. additionadded to effect dissolution
  9. customThe solvent was removed under reduced pressure
  10. dissolutionthe product was twice dissolved in ethanol
  11. concentrationconcentrated to a small volume under reduced pressure to azeotropically remove water
  12. customThe title compound was recrystallized from ethanol and hexane (28.8 g)

Sources & evidence

ORD record
ord-98fbbf205b954765abec2a43e450a43f
Source dataset
uspto-grants-2005_02
Patent number
US06852727B2

Reaction notes

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