Dimethylformamide → 4-(4-Fluorophenyl)pyridine-3-carbaldehyde;hydrochloride

HRID 2248427Notes

Reaction equation

HRID 2248427 reaction equation
[CH:1]([C:3]1[CH:4]=[N:5][CH:6]=[CH:7][C:8]=1[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)=[O:2].C(Cl)(=O)C([Cl:18])=O.CN(C)C=O.CC(C1C=CC([F:35])=CC=1)=C.Cl([O-])(=O)(=O)=O.[Na+]>ClCCCl.ClC(Cl)C>[ClH:18].[F:35][C:12]1[CH:11]=[CH:10][C:9]([C:8]2[CH:7]=[CH:6][N:5]=[CH:4][C:3]=2[CH:1]=[O:2])=[CH:14][CH:13]=1

Participants

8

Reactant 5

HCID 6228DimethylformamideHCID 65578Oxalyl chlorideHCID 676901-Fluoro-4-(isopropenyl)benzeneHCID 522606Sodium PerchlorateHCID 131605444-Phenylpyridine-3-carbaldehyde

Product 1

HCID 199963064-(4-Fluorophenyl)pyridine-3-carbaldehyde;hydrochlorideYield 76%

Reagents, catalysts & solvents 2

HCID 111,2-DichloroethaneSolventHCID 63651,1-DichloroethaneSolvent

Conditions

Temperature
100 °C

Procedure

The title compound was prepared following the method described in the literature (C. Jutz, W. Muller and E. Muller, Chem. Ber., 1966 99, 2479) for 3-formyl-4-phenylpyridine. ##STR10## Oxalyl chloride (34 ml; 0.39 moles) was added to a stirred solution of dimethylformamide (33 ml; 0.42 moles) in 1,2-dichloroethane (50 ml). To the resulting mixture was added α-methyl-p-fluorostyrene (13.6 g; 0.1 moles) in dichloroethane (20 ml) and the mixture refluxed for 3 hours. After removal of solvent by distillation under reduced pressure, water (150 ml) was added to give a dark brown solution. An aqueous solution of sodium perchlorate was added to this solution causing the di-iminium perchlorate (2) to precipitate. This was filtered off, washed with water, added to an aqueous solution of ammonium chloride (24 g in 190 ml of water) and heated at 100° C. for 1 hour. After allowing to cool, the reaction mixture was extracted with chloroform and the organic layer separated, washed with water, and ethereal HCl added causing the title compound (3) to precipitate as buff coloured crystals (18g; 76% yield based on styrene (1))

Workup

  1. temperaturethe mixture refluxed for 3 hours
  2. customAfter removal of solvent
  3. distillationby distillation under reduced pressure, water (150 ml)
  4. additionwas added
  5. customto give a dark brown solution
  6. customto precipitate
  7. filtrationThis was filtered off
  8. washwashed with water
  9. additionadded to an aqueous solution of ammonium chloride (24 g in 190 ml of water)
  10. temperatureto cool
  11. extractionthe reaction mixture was extracted with chloroform
  12. customthe organic layer separated
  13. washwashed with water, and ethereal HCl
  14. additionadded
  15. customto precipitate as buff coloured crystals (18g; 76% yield based on styrene (1))

Sources & evidence

ORD record
ord-6426822a8a014b118e61e607fe19b15f
Source dataset
uspto-grants-1991_08
Patent number
US05039803

Reaction notes

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