Acetone → Pyrido[2,3-d]pyrimidine-6-carboxaldehyde, 2,4-diamino-

HRID 1388497

反応式

HRID 1388497 の反応式
P(Cl)(Cl)(Cl)=O.CN(C)[CH:8]=[O:9].BrCC(O)=O.[NH2:16][C:17]1[N:22]=[C:21]([NH2:23])[CH:20]=[C:19]([NH2:24])[N:18]=1.[CH3:25][C:26]([CH3:28])=O>Cl.CO>[NH2:16][C:17]1[N:18]=[C:19]([NH2:24])[C:20]2[CH:28]=[C:26]([CH:8]=[O:9])[CH:25]=[N:23][C:21]=2[N:22]=1

参加物

8

反応物 5

HCID 180AcetoneHCID 6227Bromoacetic AcidHCID 6228DimethylformamideHCID 138632,4,6-TriaminopyrimidineHCID 24813Phosphorus oxychloride

生成物 1

HCID 10726310Pyrido[2,3-d]pyrimidine-6-carboxaldehyde, 2,4-diamino-

試薬・触媒・溶媒 2

HCID 313Hydrochloric Acid溶媒HCID 887Methanol溶媒

実験手順

Phosphorus oxychloride (27.5 ml, 46.0 g, 300 mmol) was added over 15 minutes with stirring to N,N-dimethylformamide (11.0 g, 150 mmol), which was cooled with an ice bath. After stirring at room temperature for 1 hour, the reaction mixture was treated with bromoacetic acid (13.9 g, 100 mmol). The resulting solution, protected by a calcium chloride tube was heated at 92° C. for 10 hours and evaporated to dryness in vacuo. The colored oil (~30 g) was dissolved in water (1000 ml), and the solution was neutralized with 50% sodium hydroxide to pH 7. After addition of 2,4,6-triaminopyrimidine (5.00 g, 40.0 mmol), the solution was refluxed for 3 hours and filtered hot through a fluted filter. The filtrate was cooled and the solid that precipitated was collected by filtration and dried in vacuo over P2O5 : yield, 2.53 g (33%). Mass spectrum, m/e 189 (M+). HPLC [ 0.1 M NH4OAc (pH 3.6) --CH3OH (9:1)] indicated that this product was 86% pure. A sample (200 mg) was dissolved in 0.1 N HCl (15 ml) and diluted with acetone (225 ml) to precipitate impure III: yield, 91 mg. The filtrate was evaporated to dryness under reduced pressure and the residue was dried in vacuo over P2O5 to give compound III: yield, 128 mg; mp, gradual darkening and decomposition with white sublimate when taken to 360° C. λmax nm (ε×10-3): 0.1 N HCl --258 (16.4), 317 (9.12), 326 sh (8.42); pH 7-263 (15.0), 316 (10.1), 345 (10.8); 0.1 N NaOH --254 (13.2), 267 (13.5), 3.16 (8.56), 347 (10.0). 1H-NMR (CF3CO2D, 6% w/v), 9.48 s, 9.75 s (5 --CH, 7 -- CH), 10.21 s (6 --CHO).

後処理

  1. temperaturewas cooled with an ice bath
  2. customThe resulting solution, protected by a calcium chloride tube
  3. temperaturewas heated at 92° C. for 10 hours
  4. customevaporated to dryness in vacuo
  5. dissolutionThe colored oil (~30 g) was dissolved in water (1000 ml)
  6. temperaturethe solution was refluxed for 3 hours
  7. filtrationfiltered hot through
  8. filtrationa fluted filter
  9. temperatureThe filtrate was cooled
  10. customthe solid that precipitated
  11. filtrationwas collected by filtration
  12. dry with materialdried in vacuo over P2O5
  13. customyield
  14. customto precipitate impure III
  15. customyield
  16. customThe filtrate was evaporated to dryness under reduced pressure
  17. dry with materialthe residue was dried in vacuo over P2O5

出典と根拠

ORDレコード
ord-3c054d471d2d441c9f24a9a918ceed3b
出典データセット
uspto-grants-1984_02
特許番号
US04431805

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