Pyridine → 5'-O-(2-(2,6-dinitrophenyl)ethoxycarbonyl)thymidine

HRID 963751Notes

Reaction equation

HRID 963751 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.[N+:24]([C:27]1[CH:32]=[CH:31][CH:30]=[C:29]([N+:33]([O-:35])=[O:34])[C:28]=1[CH2:36][CH2:37][O:38][C:39](Cl)=[O:40])([O-:26])=[O:25].CC(O)C.N#N>C(Cl)Cl>[N+:24]([C:27]1[CH:32]=[CH:31][CH:30]=[C:29]([N+:33]([O-:35])=[O:34])[C:28]=1[CH2:36][CH2:37][O:38][C:39]([O:7][CH2:6][C@H:5]1[O:8][C@@H:1]([N:9]2[CH:17]=[C:15]([CH3:16])[C:13](=[O:14])[NH:12][C:10]2=[O:11])[CH2:2][C@@H:3]1[OH:4])=[O:40])([O-:26])=[O:25]

Participants

6

Reactant 4

HCID 1049PyridineHCID 5789ThymidineHCID 190827052-(2,6-Dinitrophenyl)ethoxycarbonyl chlorideHCID 86752769N2 isopropanol

Product 1

HCID 152893345'-O-(2-(2,6-dinitrophenyl)ethoxycarbonyl)thymidineYield 43.1%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-50 °C

Procedure

Thymidine (1 g, 4.13 mmol) was co-evaporated with pyridine (3×10 ml, pro analysi quality, additionally dried over molecular sieve 4 Å), dissolved in pyridine (15 ml, see above) and cooled down to -50° C. A solution of 2-(2,6-dinitrophenyl)ethoxycarbonyl chloride (1.7 g, 6.19 mmol) in CH2Cl2 (15 ml, dist. over CaH2) was added dropwise thereto for 1 h. After a further 3.5 h stirring in conditions of i-PrOH/N2 cooling (-50° to -20° C.), the mixture was diluted with CH2Cl2 (50 ml) and washed with H2O (50 ml). The aqueous phases were post-extracted with CH2Cl2 (2×50 ml). The combined organic phases were dried over Na2SO4, filtered, concentrated under reduced pressure and co-evaporated using toluene (3×50 ml). The crude product (2.66 g) was treated with CH2Cl2 /MeOH 2:1 (60 ml) at boiling temperature. The white precipitate obtained was filtered by suction and recrystallized from MeOH (25 ml). 5'-O-(2-(2,6-dinitrophenyl)ethoxycarbonyl)thymidine (855 mg, 43%) was obtained as a colorless solid. The combined filtrates were concentrated under reduced pressure to a dry state and purified by column chromatography (1.4 g crude product, 56 g SiO2 17×3 cm, CH2Cl2 /MeOH 100:5 1240 ml, 100:7 105 ml, 100:10 330 ml). 5'-O-(2-(2,6-dinitrophenyl)ethoxcarbonyl)thymidine (691 mg, 34.8%) was obtained as a colorless solid. The yield of 5'-O-(2-(2,6-dinitrophenyl)ethoxycarbonyl)thymidine totalled 1.55 g (78%)

Workup

  1. customadditionally dried over molecular sieve 4 Å),
  2. dissolutiondissolved in pyridine (15 ml, see above)
  3. washwashed with H2O (50 ml)
  4. extractionThe aqueous phases were post-extracted with CH2Cl2 (2×50 ml)
  5. dry with materialThe combined organic phases were dried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. additionThe crude product (2.66 g) was treated with CH2Cl2 /MeOH 2:1 (60 ml)
  9. customThe white precipitate obtained
  10. filtrationwas filtered by suction
  11. customrecrystallized from MeOH (25 ml)

Sources & evidence

ORD record
ord-7f56ccbd45d14ddf9c374e6332d8f6fc
Source dataset
uspto-grants-1998_06
Patent number
US05763599

Reaction notes

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