Chlorotrimethylsilane → 3'-O-benzyl-2'-deoxy-3-benzoyl-5-fluorouridine

HRID 466088Notes

Reaction equation

HRID 466088 reaction equation
[CH2:1]([O:8][C@@H:9]1[C@@H:13]([CH2:14][OH:15])[O:12][C@@H:11]([N:16]2[CH:23]=[C:22]([F:24])[C:20](=[O:21])[NH:19][C:17]2=[O:18])[CH2:10]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C[Si](C)(C)Cl.C(N(CC)CC)C.[C:37](Br)(=[O:44])[C:38]1[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=1>O1CCOCC1>[CH2:1]([O:8][C@@H:9]1[C@@H:13]([CH2:14][OH:15])[O:12][C@@H:11]([N:16]2[CH:23]=[C:22]([F:24])[C:20](=[O:21])[N:19]([C:37](=[O:44])[C:38]3[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=3)[C:17]2=[O:18])[CH2:10]1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 4

HCID 6397ChlorotrimethylsilaneHCID 8471Triethylamine2×HCID 12056Benzoyl bromideHCID 10664574Uridine, 2'-deoxy-5-fluoro-3'-O-(phenylmethyl)-

Product 1

HCID 137150613'-O-benzyl-2'-deoxy-3-benzoyl-5-fluorouridineYield 54%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

To a solution of 0.50 g of 3'-O-benzyl-2'-deoxy-5-fluorouridine in 20 ml of dioxane were added 0.75 ml of trimethylchlorosilane and 2.00 ml of triethylamine, and the mixture was stirred at room temperature for 2 hours. Then, the resulting mixture was left to stand at 60° C. for 30 minutes. To the reaction mixture were added 0.42 g of benzoyl bromide and 1.00 ml of triethylamine, and the mixture was left to stand at 60° C. for 1 hour. The solvent was distilled off and the residue was dissolved in 50 ml of ethyl acetate. Then, the solution was washed with saturated aqueous solution of sodium chloride. The ethyl acetate layer was separated and concentrated. The residue was dissolved in 30 ml of methanol and 0.5 ml of acetic acid was added thereto. The mixture was left to stand overnight. The solvent was distilled off and the residue was applied to a silica gel column to conduct gradient elution using chloroform and mixtures of methanol (up to 2%) and chloroform, giving 0.35 g of the title compound as a powder in a yield of 54%.

Workup

  1. waitThen, the resulting mixture was left
  2. waitto stand at 60° C. for 30 minutes
  3. waitthe mixture was left
  4. waitto stand at 60° C. for 1 hour
  5. distillationThe solvent was distilled off
  6. dissolutionthe residue was dissolved in 50 ml of ethyl acetate
  7. washThen, the solution was washed with saturated aqueous solution of sodium chloride
  8. customThe ethyl acetate layer was separated
  9. concentrationconcentrated
  10. dissolutionThe residue was dissolved in 30 ml of methanol
  11. addition0.5 ml of acetic acid was added
  12. waitThe mixture was left
  13. waitto stand overnight
  14. distillationThe solvent was distilled off
  15. washelution

Sources & evidence

ORD record
ord-7f7e4ddbf85541019e3aa15dd7257b95
Source dataset
uspto-grants-1992_10
Patent number
US05155113

Reaction notes

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