Oxalyl chloride → Thymine

Temperature

-55 °C

To a solution of DMSO (170μl, 2.34 mM) and CH2Cl2 (0.5 ml) at -60° C., was added 135 ml of (COCl)2 in 1 ml of CH2Cl2 dropwise over a period of 5 minutes. After 15 minutes, 3'-deoxy-4'-hydroxymethylthymidine (0.3 g, 1.17 mM), prepared, e.g., as described in Preparation 15, in 0.5 ml DMSO/0.5 ml CH2Cl2 was added slowly and the mixture stirred at -55° C. for 3 hours. After the addition of 0.65 ml TEA, the solution was removed from the cooling bath and allowed to warm to 24° C. at which temperature it was stirred for 15 minutes. The solution was filtered and the solvent was removed by evaporation. The residue was dissolved in pyridine; treated with H2NOH HCl (0.2 g, 2.9 mM), and stirred at 24° C. for 48 hours. The solvent was removed by evaporation and the residue was chromatographed on silica gel using 8% CH3OH/CH2Cl2, yielding a mixture of the 4'-α and 4'-β isomers of 3'-deoxy-4'-hydroxyiminomethylthymidine (140 mg, 0.52 mM).

1. additionwas added slowly
2. customthe solution was removed from the cooling bath
3. temperatureto warm to 24° C. at which temperature it
4. stirringwas stirred for 15 minutes
5. filtrationThe solution was filtered
6. customthe solvent was removed by evaporation
7. dissolutionThe residue was dissolved in pyridine
8. additiontreated with H2NOH HCl (0.2 g, 2.9 mM)
9. stirringstirred at 24° C. for 48 hours
10. customThe solvent was removed by evaporation
11. customthe residue was chromatographed on silica gel using 8% CH3OH/CH2Cl2
12. customyielding

ORD record

ord-ffcbf5361d1b432a9e8964baa07d0319

Source dataset

uspto-grants-1993_03

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US05192749