Malononitrile → 2-Amino-5-(4-chlorophenyl)pyridine-3-carbonitrile

HRID 1980310Notes

Reaction equation

HRID 1980310 reaction equation
C[O-].[Na+].[C:4](#[N:8])[CH2:5][C:6]#[N:7].Cl([O-])(=O)(=O)=O.[Cl:14][C:15]1[CH:20]=[CH:19][C:18]([C:21](=[CH:26]N(C)C)[CH:22]=[N+:23](C)C)=[CH:17][CH:16]=1.[OH-].[NH4+]>CO.N1C=CC=CC=1>[NH2:7][C:6]1[C:5]([C:4]#[N:8])=[CH:26][C:21]([C:18]2[CH:17]=[CH:16][C:15]([Cl:14])=[CH:20][CH:19]=2)=[CH:22][N:23]=1

Participants

7

Reactant 4

HCID 8010MalononitrileHCID 14923Ammonium HydroxideHCID 10942334Sodium MethoxideHCID 72970776N-[2-(4-chlorophenyl)-3-(dimethylamino)-2-propenylidene]-N-methylmethanaminium perchlorate

Product 1

HCID 132426422-Amino-5-(4-chlorophenyl)pyridine-3-carbonitrile

Reagents, catalysts & solvents 2

HCID 887MethanolSolvent2×HCID 1049PyridineSolvent

Procedure

Sodium methoxide (16.2 grams) in 300 ml methanol and malononitrile (19.8 grams) in 50-100 ml methanol were added to N-[2-(4-chlorophenyl)-3-(dimethylamino)-2-propenylidene]-N-methylmethanaminium perchlorate (101.1 grams) in 300 ml pyridine at 0° C. in an ice-alcohol bath. The reaction mixture was stirred at room temperature for about 20 hours and then recooled to 0° C. Ammonium hydroxide (120 ml) was added and after three hours, a copious precipitate formed. The solid was filtered, washed with water, and shown by NMR to be the desired product, yield 44 grams, m.p. 202°-204° C. Addition of 600-800 ml of water to the filtrate gave additional product although impurities were present.

Workup

  1. customrecooled to 0° C
  2. customa copious precipitate formed
  3. filtrationThe solid was filtered
  4. washwashed with water
  5. additionAddition of 600-800 ml of water to the filtrate
  6. customgave additional product although impurities

Sources & evidence

ORD record
ord-24a34b8d03af4f7aa8f2a5198fd8aa71
Source dataset
uspto-grants-1985_04
Patent number
US04508722

Reaction notes

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