Phenylacetic Acid → Chloro-N,N-dimethylformiminium chloride

HRID 477463Notes

Reaction equation

HRID 477463 reaction equation
O(Cl)[Cl:2].[C:4]1([CH2:10][C:11](O)=O)[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.[OH-].[Na+].O.[NH2:17][NH2:18].[CH3:19][N:20]([CH:22]=O)[CH3:21]>>[CH3:21][N+:20]([CH3:19])=[CH:22][Cl:2].[Cl-:2].[C:4]1([C:10]2[CH:11]=[N:17][NH:18][CH:19]=2)[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1

Participants

7

Reactant 5

HCID 999Phenylacetic AcidHCID 6228Dimethylformamide2×HCID 14798Sodium HydroxideHCID 24646Chlorine monoxideHCID 24654Hydrazine hydrate (1:1)

Product 2

HCID 77311Chloro-N,N-dimethylformiminium chlorideHCID 1391064-Phenylpyrazole

Conditions

Temperature
70 °C

Procedure

Vilsmeier reagent was prepared by adding 84 mL (0.9 mol) of phosphous oxychloride to 81g (1.1 mol) of DMF with cooling. The reagent was stirred 5 min. and 40.8 g (0.3 mol) of phenylacetic acid in 150 mL of DMF was added dropwise. The mixture was heated at 70° C. for 18 hr, poured onto ice, made basic with 35% aqueous NaOH, filtered free of a solid by-product, and extracted into methylene chloride. The methylene chloride solution was dried over magnesium sulfate and stripped. The residue of 2-phenyl-3-(dimethylamino)acrolein was dissolved in about 350 mL of ethanol and 0.75 mol of hydrazine hydrate was added. The mixture was stirred at room temperature 18 hr and the solid product was filtered off. It was recrystallized from ethanol to yield 35g of 4-phenyl-1H-pyrazole.

Workup

  1. temperaturewith cooling
  2. additionpoured onto ice
  3. filtrationfiltered free of a solid by-product
  4. extractionextracted into methylene chloride
  5. dry with materialThe methylene chloride solution was dried over magnesium sulfate
  6. dissolutionThe residue of 2-phenyl-3-(dimethylamino)acrolein was dissolved in about 350 mL of ethanol
  7. stirringThe mixture was stirred at room temperature 18 hr
  8. filtrationthe solid product was filtered off
  9. customIt was recrystallized from ethanol

Sources & evidence

ORD record
ord-a6eac38e8cb446b3977906e63b656a80
Source dataset
uspto-grants-1989_12
Patent number
US04888352

Reaction notes

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