Dimethylformamide → 6-Oxo-1,6-dihydro-3,4'-bipyridine-5-carbonitrile

HRID 1105993Notes

Reaction equation

HRID 1105993 reaction equation
[N:1]1[CH:6]=[CH:5][C:4]([CH3:7])=[CH:3][CH:2]=1.P(Cl)(Cl)(Cl)=O.[C:13](Cl)(Cl)=[O:14].S(Cl)(Cl)=O.S(Cl)(Cl)(=O)=O.P(Cl)(Cl)Cl.P(Cl)(Cl)(Cl)(Cl)Cl.P(Br)(Br)Br.C(Br)(Br)=O.C(Cl)(Cl)=S.C[N:49]([CH3:52])C=O>O>[C:2]([C:3]1[C:13](=[O:14])[NH:49][CH:52]=[C:7]([C:4]2[CH:5]=[CH:6][N:1]=[CH:2][CH:3]=2)[CH:4]=1)#[N:1]

Participants

13

Reactant 11

HCID 6228DimethylformamideHCID 6371PhosgeneHCID 79634-Methylpyridine3×HCID 10040ThiophosgeneHCID 24386Thionyl ChlorideHCID 24387Phosphorus trichlorideHCID 24614Phosphorus tribromideHCID 24648Sulfuryl chlorideHCID 24813Phosphorus oxychlorideHCID 24819Phosphorus pentachlorideHCID 79057Carbonyl bromide

Product 1

HCID 1319896-Oxo-1,6-dihydro-3,4'-bipyridine-5-carbonitrile

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

The process which comprises the steps of reacting 4-picoline below about 30° C. with at least three mole equivalents per mole of 4-picoline of an inorganic acid halide selected from phosphorus oxychloride, phosgene, thionyl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide, carbonyl dibromide or thiophosgene and about five to twenty volumes of dimethylformamide per volume of 4-picoline, adding the reaction mixture to cold water and adjusting the pH to about 8.0 while keeping the temperature below about 30° C., filtering off the precipitated inorganic cationic salt, treating the aqueous filtrate which contains N-[3-dimethylamino-2-(4-pyridinyl)-2-propenylidene]-N-methylmethaniminium salt with at least about 30-35% molar excess of α-cyanoacetamide and at least three mole equivalents of base still keeping the temperature below about 30° C., and then isolating either 5-cyano-[3,4'-bipyridin]-6(1H)-one as its inorganic cationic salt or, after neutralization, in its free base form.

Workup

  1. customthe temperature below about 30° C.
  2. filtrationfiltering off the precipitated inorganic cationic salt
  3. additiontreating the aqueous filtrate which
  4. customthe temperature below about 30° C.

Sources & evidence

ORD record
ord-91020b82470240b2909c915a5f3b3640
Source dataset
uspto-grants-1982_01
Patent number
US04310670

Reaction notes

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