反应详情

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).

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