Reaction #4987

Reaction equation

KBr

5'-O-(p-toluenesulfonyl)thymidine

monomethylamine

monomethylamine

→

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

Solvents

water

Conditions

Workup

1. 1
   Othercondensed
2. 2
   OtherThe vessel was sealed
3. 3
   TemperatureThe vessel was cooled
4. 4
   Otherto evaporate
5. 5
   OtherThe remaining contents of the vessel were removed
6. 6
   Washby rinsing with water
7. 7
   WashThe column was washed with water until the washings
8. 8
   WashThe product was then eluted with 1N aqueous ammonium hydroxide
9. 9
   Otherthe 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
    OtherA satisfactory combustion analysis could not be obtained for this material

Procedure

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).

Source