Carbon Dioxide → 4-(1-Formyl-2-oxoethyl)benzoic acid

HRID 352695Notes

Reaction equation

HRID 352695 reaction equation
O=P(Cl)(Cl)Cl.[C:6](=[O:8])=[O:7].[CH4:9].[C:10](=[O:13])([O-])[O-].[K+].[K+].[OH-].[Na+].Cl.Cl.N[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1.CN(C)[CH:29]=[O:30]>O>[C:6]([C:24]1[CH:25]=[CH:26][C:21]([CH:9]([CH:10]=[O:13])[CH:29]=[O:30])=[CH:22][CH:23]=1)([OH:8])=[O:7]

Participants

10

Reactant 8

HCID 280Carbon DioxideHCID 297MethaneHCID 313Hydrochloric AcidHCID 6228DimethylformamideHCID 8870Benzenamine hydrochloride (1:1)HCID 11430Potassium CarbonateHCID 14798Sodium HydroxideHCID 24813Phosphorus oxychloride

Product 1

HCID 880486244-(1-Formyl-2-oxoethyl)benzoic acid

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Procedure

28 mL of POCl3 are added to 39 mL stirred, cooled N,N-dimethylformamide, followed by 16 g of p-cyanophenylacetic. After 1 hour, the reaction mixture is heated at 80-90° C. until carbon dioxide is no longer evolved, about 6 hours. The mixture is cooled to room temperature, mixed within 100 g of ice, and the aqueous mixture is shaken with a small amount of charcoal. The aqueous solution is made basic with potassium carbonate and extracted 3 times with 200 mL portions of dichloromethane. The combined organic layers are washed with distilled water, dried with sodium sulphate and evaporated to a dark oil. This oil is subjected to basic hydrolysis to produce the free dihaldehyde and at the same time convert the nitrile to the corresponding carboxylate. Thus, the oil is suspended in 100 mL of water and 25 mL of 50% aqueous NaOH are added with stirring. The mixture is heated at 70° C. until a homogenous aqueous solution results. The solution is neutralised with concentrated hydrochloric acid and 25 g of aniline hydrochloride dissolved in 100 mL of water are added. The yellow orange precipitate is collected on a fritted glass filter and dried in the oven at 50° C.

Workup

  1. waitis no longer evolved, about 6 hours
  2. extractionextracted 3 times with 200 mL portions of dichloromethane
  3. washThe combined organic layers are washed with distilled water
  4. dry with materialdried with sodium sulphate
  5. customevaporated to a dark oil
  6. customThis oil is subjected to basic hydrolysis
  7. customto produce the free dihaldehyde
  8. stirringwith stirring
  9. temperatureThe mixture is heated at 70° C. until a homogenous aqueous solution
  10. customresults
  11. additionare added
  12. customThe yellow orange precipitate is collected on a fritted glass
  13. filtrationfilter
  14. customdried in the oven at 50° C.

Sources & evidence

ORD record
ord-9b6b288ba29c4881b028d7ad64cf785b
Source dataset
uspto-grants-2004_06
Patent number
US06747159B2

Reaction notes

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