Dimethylformamide → 6-(2,6-Dichlorophenyl)-8-methyl-2-(methylthio)pyrido[2,3-d]pyrimidin-7(8H)-imine

HRID 3171Notes

Reaction equation

HRID 3171 reaction equation
C(=O)([O-])[O-].[K+].[K+].[CH3:7][NH:8][C:9]1[C:14]([CH:15]=O)=[CH:13][N:12]=[C:11]([S:17][CH3:18])[N:10]=1.[Cl:19][C:20]1[CH:25]=[CH:24][CH:23]=[C:22]([Cl:26])[C:21]=1CC#N.C(O[CH2:34][CH3:35])(=O)C.C[N:37](C)C=O>C(Cl)Cl>[Cl:19][C:20]1[CH:25]=[CH:24][CH:23]=[C:22]([Cl:26])[C:21]=1[C:35]1[C:34](=[NH:37])[N:8]([CH3:7])[C:9]2[N:10]=[C:11]([S:17][CH3:18])[N:12]=[CH:13][C:14]=2[CH:15]=1

Participants

7

Reactant 5

HCID 6228DimethylformamideHCID 8857Ethyl AcetateHCID 11430Potassium CarbonateHCID 76678(2,6-Dichlorophenyl)acetonitrileHCID 106075204-(Methylamino)-2-(methylthio)pyrimidine-5-carbaldehyde

Product 1

HCID 108078276-(2,6-Dichlorophenyl)-8-methyl-2-(methylthio)pyrido[2,3-d]pyrimidin-7(8H)-imineYield 40%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
125 °C

Procedure

Powdered potassium carbonate (0.8 g; 5.8 mmol) was added to a solution of 0.220 g (1.2 mmol) of the aldehyde from Example 18 and 0.235 g (1.26 mmol) (ca. 5% excess) of 2,6-dichlorophenylacetonitrile in 2.0 mL of dimethylformamide. The mixture was heated with stirring at 125° C. for 6 hours. Ethyl acetate (5 mL) was added to the cooled mixture, and the solids were filtered and washed with ethyl acetate. The filtrate was concentrated under reduced pressure. The residual gum was triturated with 10 mL of water, and the resulting solid was filtered, washed well with water, and dried. This crude material was chromatographed by placing a chloroform solution on a silica gel column wet with chloroform. The column was eluted with 1:1 (v/v) hexane:ethyl acetate, collecting the fractions that contain the Rf 0.25 spot on tlc (1:1 hexane:ethyl acetate). Evaporation of the solvents gave a solid. The solid product was dissolved in about 0.5 mL of methylene chloride. Crystals develop. Petroleum ether (ca. 2 mL) was added, and the crystals were filtered to provide 0.168 g (40%) of 6-(2,6-dichlorophenyl)-8-methyl-2-methylsulfanyl-8H-pyrido[2,3-d]pyrimidin-7-ylideneamine, mp 198°-200° C.

Workup

  1. temperatureThe mixture was heated
  2. filtrationthe solids were filtered
  3. washwashed with ethyl acetate
  4. concentrationThe filtrate was concentrated under reduced pressure
  5. customThe residual gum was triturated with 10 mL of water
  6. filtrationthe resulting solid was filtered
  7. washwashed well with water
  8. customdried
  9. customThis crude material was chromatographed
  10. washThe column was eluted with 1:1 (v/v) hexane
  11. customethyl acetate, collecting the fractions that
  12. customEvaporation of the solvents
  13. customgave a solid
  14. filtrationthe crystals were filtered

Sources & evidence

ORD record
ord-a7d5dc196a1f4db59fce7d32888d8b45
Source dataset
uspto-grants-1998_03
Patent number
US05733914

Reaction notes

Loading…