Ethanol → HCID 13458456, compound

HRID 1981151Notes

Reaction equation

HRID 1981151 reaction equation
CN(C)C=O.S(Cl)([Cl:8])=O.[NH2:10][C:11]1[N:12]=[C:13]([NH2:34])[C:14]2[C:20]([CH3:21])=[C:19]([CH2:22][C:23]3[CH:28]=[CH:27][C:26]([O:29][CH3:30])=[C:25]([O:31][CH3:32])[CH:24]=3)[C:18](=O)[NH:17][C:15]=2[N:16]=1.C(O)C>C(Cl)(Cl)Cl>[NH2:10][C:11]1[N:12]=[C:13]([NH2:34])[C:14]2[C:20]([CH3:21])=[C:19]([CH2:22][C:23]3[CH:28]=[CH:27][C:26]([O:29][CH3:30])=[C:25]([O:31][CH3:32])[CH:24]=3)[C:18]([Cl:8])=[N:17][C:15]=2[N:16]=1

Participants

6

Reactant 4

HCID 702EthanolHCID 6228DimethylformamideHCID 24386Thionyl ChlorideHCID 13458455HCID 13458455, compound

Product 1

HCID 13458456HCID 13458456, compoundYield 23.1%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent3×

Conditions

Temperature
0 °C

Procedure

To a solution of dimethylformamide (17.5 g) in chloroform (75 ml) was added thionyl chloride (28.6 g) in chloroform (25 ml) at 0°-5° C. The reaction mixture was allowed to heat to 55°-60° for about 5 minutes and cooled to 0° C. To the reaction mixture was added over a 20 minute period at 0° C. 2,4-diamino-5-methyl-6-(3,4-dimethoxybenzyl)-7-oxo-7,8-dihydropyrido[2,3-d]-pyrimidine (8.2 g). Chloroform (50 ml) was added, and the mixture was heated at reflux for 2.5 hours and cooled. Ethanol in base (50 ml) was added. The resulting brown product was collected by filtration, treated with 2N sodium hydroxide and recrystallized from ethanol to give 7.6 g of crude product. Additional recrystallization from ethanol-water gave 2,4-diamino-5-methyl-6-(3,4-dimethoxybenzyl)-7-chloropyrido[2,3-d]pyrimidine (2 g), m.p. 224°-225° C. (dec.). This was added to ethanol (250 ml) containing potassium hydroxide (0.2 g), 5% palladium on charcoal catalyst (Pd/C, 0.1 g) was added and hydrogenation commenced. Reduction was complete after 4 hours in a Parr low-pressure apparatus at 35-40 psi and gave 2,4-diamino-6-(3,4-dimethoxybenzyl)-5-methylpyrido[2,3-d]pyrimidine (0.1 g), m.p. 265°-268° C. (dec.).

Workup

  1. temperatureto heat to 55°-60° for about 5 minutes
  2. additionTo the reaction mixture was added over a 20 minute period at 0° C
  3. temperaturethe mixture was heated
  4. temperatureat reflux for 2.5 hours
  5. temperaturecooled
  6. filtrationThe resulting brown product was collected by filtration
  7. additiontreated with 2N sodium hydroxide
  8. customrecrystallized from ethanol
  9. customto give 7.6 g of crude product
  10. customAdditional recrystallization from ethanol-water

Sources & evidence

ORD record
ord-0f4455cb8e6d4637bd52e28789755c27
Source dataset
uspto-grants-1985_04
Patent number
US04512992

Reaction notes

Loading…