Reaktion #1701488

Reaktionsgleichung

pyrimidine

2-Amino-6-chloro-4-hydroxy-5-nitropyrimidine

triethylamine

1,2-diamino-2-phenylpropane

→

monohydrochloride

Ausbeute 95.0%

2-Amino-6-(2-amino-2-phenylpropylamino)-4-hydroxy-5-nitropyrimidine monohydrochloride

Ausbeute 95.0%

Lösungsmittel

ethanol

ethanol

ethanol

Reaktionsbedingungen

Aufarbeitung

1. 1
   workup.ADDITIONwas added
2. 2
   Temperaturmaintained
3. 3
   Temperaturat reflux as a light yellow precipitate
4. 4
   Sonstigeformed
5. 5
   Sonstigea marked slowing of the condensation after a little over one-half of the reactants
6. 6
   Sonstigehad been consumed
7. 7
   Waschen(Partisil SCX column (25×0.46 cm) eluted with 0.1M ammonium hydroxide made to pH 3.3 with formic acid/methanol, 3:2 v/v)
8. 8
   SonstigeCompletion of the reaction to within 97% utilization of the diamine
9. 9
   Temperaturthe reaction being refluxed an additional hour
10. 10
    workup.WAITAfter being kept overnight at -15° C.
11. 11
    Sonstigethe majority of the somewhat gelatinous product was collected by centrifugation
12. 12
    Waschenwashed with 10 ml cold ethanol
13. 13
    SonstigeA second crop of equal purity was collected
14. 14
    workup.WAITto stand for an additional 5 days at -15° C.
15. 15
    Waschensimilarly washed
16. 16
    TrocknenThese materials dried under vacuum in the presence of P2O5

Vorschrift

2-Amino-6-chloro-4-hydroxy-5-nitropyrimidine (0.626 g; 3.0 mmole) was dissolved in 130 ml of refluxing absolute ethanol and 0.45 g of 1,2-diamino-2-phenylpropane free-base (3.0 mmole) was added all at once dissolved in 8 ml of absolute ethanol. The mixture was stirred and maintained at reflux as a light yellow precipitate formed. Analysis by HPLC at 30 minutes showed a marked slowing of the condensation after a little over one-half of the reactants had been consumed. (Partisil SCX column (25×0.46 cm) eluted with 0.1M ammonium hydroxide made to pH 3.3 with formic acid/methanol, 3:2 v/v). Completion of the reaction to within 97% utilization of the diamine was accomplished by addition of 3.6 ml of 1M triethylamine in absolute ethanol (3.6 mmole) followed by 0.063 g of the above pyrimidine, the reaction being refluxed an additional hour. After being kept overnight at -15° C. the majority of the somewhat gelatinous product was collected by centrifugation, washed with 10 ml cold ethanol, and finally, twice with 30 ml each of ethyl ether. A second crop of equal purity was collected after allowing the mother liquor supernate to stand for an additional 5 days at -15° C., and similarly washed. These materials dried under vacuum in the presence of P2O5 gave 0.97 g (0.889+0.081) of the monohydrochloride salt for a yield of 95% based upon diamine.

Quelle