Pyridine → 5'-O-(2-(4-chloro-2-nitrophenyl)ethoxycarbonyl)thymidine

HRID 963760Notes

Reaction equation

HRID 963760 reaction equation
[C@@H:1]1([N:9]2[CH:17]=[C:15]([CH3:16])[C:13](=[O:14])[NH:12][C:10]2=[O:11])[O:8][C@H:5]([CH2:6][OH:7])[C@@H:3]([OH:4])[CH2:2]1.N1C=CC=CC=1.[Cl:24][C:25]1[CH:30]=[CH:29][C:28]([CH2:31][CH2:32][O:33][C:34](Cl)=[O:35])=[C:27]([N+:37]([O-:39])=[O:38])[CH:26]=1.CC(O)C.N#N>C(Cl)Cl>[Cl:24][C:25]1[CH:30]=[CH:29][C:28]([CH2:31][CH2:32][O:33][C:34]([O:7][CH2:6][C@H:5]2[O:8][C@@H:1]([N:9]3[CH:17]=[C:15]([CH3:16])[C:13](=[O:14])[NH:12][C:10]3=[O:11])[CH2:2][C@@H:3]2[OH:4])=[O:35])=[C:27]([N+:37]([O-:39])=[O:38])[CH:26]=1

Participants

6

Reactant 4

HCID 1049PyridineHCID 5789ThymidineHCID 190827062-(4-Chloro-2-nitrophenyl)ethoxycarbonyl chlorideHCID 86752769N2 isopropanol

Product 1

HCID 152893385'-O-(2-(4-chloro-2-nitrophenyl)ethoxycarbonyl)thymidineYield 75.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-30 °C

Procedure

Thymidine (150 mg, 0.62 mmol) was co-evaporated with pyridine (2×5 ml, pro analysi quality, additionally dried over molecular sieve 4 Å), dissolved in pyridine and cooled to -30° C. A solution of 2-(4-chloro-2-nitrophenyl)ethoxycarbonyl chloride (255 mg, 0.97 mmol) in CH2Cl2 (3 ml, dist. over CaH2) was added dropwise thereto for 5 min. After being stirred for 4 h in conditions of i-PrOH/N2 cooling (-30° to -15° C.), the mixture was diluted with CH2Cl2 (30 ml) and washed with H2O (30 ml). The aqueous phase was post-extracted with CH2Cl2 (2×30 ml). The combined organic phases were dried over MgSO4, filtered and co-evaporated with toluene (4×10 ml) and CH2Cl2 (20 ml). The crude product was purified by column chromatography (SiO2 15×3 cm, solvent: CH2Cl2 /MeOH 100:7 700 ml). 5'-O-(2-(4-chloro-2-nitrophenyl)ethoxycarbonyl)thymidine (219 mg, 75% ) was obtained as a colorless solid.

Workup

  1. customadditionally dried over molecular sieve 4 Å),
  2. dissolutiondissolved in pyridine
  3. washwashed with H2O (30 ml)
  4. extractionThe aqueous phase was post-extracted with CH2Cl2 (2×30 ml)
  5. dry with materialThe combined organic phases were dried over MgSO4
  6. filtrationfiltered
  7. customThe crude product was purified by column chromatography (SiO2 15×3 cm, solvent: CH2Cl2 /MeOH 100:7 700 ml)

Sources & evidence

ORD record
ord-c18e8617897f43578794f8d3496e5bf2
Source dataset
uspto-grants-1998_06
Patent number
US05763599

Reaction notes

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