Hydrochloric Acid → HCID 19864569, compound

HRID 1200038Notes

Reaction equation

HRID 1200038 reaction equation
[C:1]1([C:7]2[C:12]([C:13]([OH:15])=[O:14])=[CH:11][N+:10]([O-])=[CH:9][CH:8]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[C-]#N.[Na+].[CH2:20]([NH:22]CC)C.Cl[Si](C)(C)C.Cl>CN(C)C=O.O>[C:13]([C:12]1[C:7]([C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)=[CH:8][C:9]([C:20]#[N:22])=[N:10][CH:11]=1)([OH:15])=[O:14]

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 6397ChlorotrimethylsilaneHCID 8021DiethylamineHCID 8929Sodium CyanideHCID 54061620HCID 54061620, compound

Product 1

HCID 19864569HCID 19864569, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

To a solution of 4-phenylnicotinic acid N-oxide (8.4 g, 0.04 mol), sodium cyanide (6.45 g, 0.13 mol) and diethylamine (26.2 ml, 0.19 mol) in absolute dimethylformamide (200 ml), chlorotrimethylsilane (23.8 ml, 0.19 mol) is added. The reaction mixture is then heated for 26 h at 100°-110°. After cooling, the solution is poured into 200 ml of water and the pH is adjusted to pH 4 by the addition of concentrated HCl. The mixture is extracted with ethyl acetate and the extracts are concentrated. The dark residue is dissolved in 150 ml of ethyl acetate and extracted with a saturated solution of sodium hydrogen carbonate. This latter extract is acidified with concentrated HCl to pH 4 and extracted again with ethyl acetate. The combined ethyl acetate extracts are evaporated to dryness, and the residue is chromatographed in ethyl acetate/methanol (1:1) on Florisil® [magnesium silicate (30-60 mesh, Fluka, Buchs, CH)]to yield 5-carboxy-2-cyano-4-phenyl-pyridine, m.p. 270°-272°, Rf =0.6.

Workup

  1. temperatureThe reaction mixture is then heated for 26 h at 100°-110°
  2. temperatureAfter cooling
  3. extractionThe mixture is extracted with ethyl acetate
  4. concentrationthe extracts are concentrated
  5. dissolutionThe dark residue is dissolved in 150 ml of ethyl acetate
  6. extractionextracted with a saturated solution of sodium hydrogen carbonate
  7. extractionThis latter extract
  8. extractionextracted again with ethyl acetate
  9. customThe combined ethyl acetate extracts are evaporated to dryness
  10. customthe residue is chromatographed in ethyl acetate/methanol (1:1) on Florisil® [magnesium silicate (30-60 mesh, Fluka, Buchs, CH)]to

Sources & evidence

ORD record
ord-86256260b7e040dd82d07a2f9f8ab2e8
Source dataset
uspto-grants-1990_02
Patent number
US04904675

Reaction notes

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