Reaktion #4987

Reaktionsgleichung

KBr

5'-O-(p-toluenesulfonyl)thymidine

monomethylamine

monomethylamine

→

5'-Deoxy-5'-(methyl-amino)-thymidine

Lösungsmittel

water

Reaktionsbedingungen

Aufarbeitung

1. 1
   Sonstigecondensed
2. 2
   SonstigeThe vessel was sealed
3. 3
   TemperaturThe vessel was cooled
4. 4
   Sonstigeto evaporate
5. 5
   SonstigeThe remaining contents of the vessel were removed
6. 6
   Waschenby rinsing with water
7. 7
   WaschenThe column was washed with water until the washings
8. 8
   WaschenThe product was then eluted with 1N aqueous ammonium hydroxide
9. 9
   Sonstigethe resulting solid chromatographed on a column (6.5×20 cm) of silica gel with methylene chloride/methanol/concentrated aqueous ammonium hydroxide (85:13:2) as the eluting solvent
10. 10
    workup.ADDITIONThe product containing fractions
11. 11
    SonstigeA satisfactory combustion analysis could not be obtained for this material

Vorschrift

5'-O-(p-toluenesulfonyl)thymidine (19.8 g, 50 mmol) was placed in a pressure vessel into which monomethylamine (250 g) was condensed. The vessel was sealed and allowed to stand at room temperature for 3 days. The vessel was cooled, opened, and the monomethylamine allowed to evaporate. The remaining contents of the vessel were removed by rinsing with water. The aqueous solution was passed through a column (6.5×20 cm) of AG50Wx8 ion-exchange resin (H+ form). The column was washed with water until the washings were neutral. The product was then eluted with 1N aqueous ammonium hydroxide. The eluent was stripped down and the resulting solid chromatographed on a column (6.5×20 cm) of silica gel with methylene chloride/methanol/concentrated aqueous ammonium hydroxide (85:13:2) as the eluting solvent. The product containing fractions were stripped down, then taken up in water and lyophilized. The product was a pale-yellow, amorphous solid (8.81 g, 69%). A satisfactory combustion analysis could not be obtained for this material.) [α]D25 (c=1.0 in water): +25.9 deg. ir (KBr): cm-1 1693, 1472, 1273, 1076. NMR (DMSO-d6): δ 1.790 (d, 3H), 2.051 (ddd, 13.4, 6.3, 3.5 hz, 1H), 2.142 (dt, 13.4, 6.9 hz, 1H), 2.314 (s, 3H), 2.658 (d, 5.5 hz, 2H), 3.775 (td, 5.3, 3.2 hz, 1H), 4.171 (dt, 6.3, 3.2 hz, 1H), 6.134 (t, 6.9 hz, 1H) and d7.639 (s, 1H).

Quelle