Methanol → HCID 22853714, compound

HRID 234973Notes

Reaction equation

HRID 234973 reaction equation
[CH3:1][C:2]1[C:3](=[O:17])[NH:4][C:5](=[O:16])[N:6]([CH:15]=1)[C@@H:7]1[O:14][C@H:11]([CH2:12][OH:13])[CH2:10][C@H:8]1[OH:9].[Si:18](Cl)([C:21]([CH3:24])([CH3:23])[CH3:22])([CH3:20])[CH3:19].CO>N1C=CC=CC=1.C(OCC)(=O)C>[Si:18]([O:13][CH2:12][C@H:11]1[O:14][C@@H:7]([N:6]2[CH:15]=[C:2]([CH3:1])[C:3](=[O:17])[NH:4][C:5]2=[O:16])[C@H:8]([OH:9])[CH2:10]1)([C:21]([CH3:24])([CH3:23])[CH3:22])([CH3:20])[CH3:19]

Participants

6

Reactant 3

HCID 887Methanol2×HCID 28928tert-Butyldimethylsilyl chlorideHCID 98812845-Methyl-3'-deoxyuridine

Product 1

HCID 22853714HCID 22853714, compoundYield 84.4%

Reagents, catalysts & solvents 2

HCID 1049PyridineSolventHCID 8857Ethyl AcetateSolvent

Procedure

5-Methyl-3'-deoxyuridine, from Step 1, was dissolved in 150 mL of dry pyridine and 3.6 g (24 mmol) of t-butyldimethylsilyl chloride was added in 4 portions at 4 times (t): t=0 h, t=2 h, t=3 h and at t=3.75 h. After 4.5 h, 8 mL of methanol was added to the reaction mixture and the reaction mixture was stirred for 0.5 h, then concentrated under reduced pressure to approximately 25% of volume. The concentrated reaction mixture was diluted with ethyl acetate, washed with dilute aqueous sodium bicarbonate solution and then concentrated under reduced pressure. The residue was purified by column chromatography on a 5 cm×37 cm silica gel column eluted with 90% ethyl acetate in hexane. The fractions containing the desired product were combined and concentrated in vacuo to give 7.27 g (84.4% yield based on 24.19 mmol of 2',5'-bis(O-(4"-chloro)benzoyl)-5-methyl-3'-deoxyuridine) of 5'-O-(t-butyldimethylsilyl)-5-methyl-3'-deoxyuridine, [α]D23 =-19.6° (c, 1.42, MeOH). Analysis calculated for C16H28N2O5Si: C, 53.98; H, 7.91; N, 7.87. Found: C, 54.01; H, 7.85; N, 7.79.

Workup

  1. customt=0 h, t=2 h, t=3 h
  2. customat t=3.75 h
  3. concentrationconcentrated under reduced pressure to approximately 25% of volume
  4. customThe concentrated reaction mixture
  5. washwashed with dilute aqueous sodium bicarbonate solution
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was purified by column chromatography on a 5 cm×37 cm silica gel column
  8. washeluted with 90% ethyl acetate in hexane
  9. additionThe fractions containing the desired product
  10. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-3bd0c199afd1446d8dfc956b2c942f06
Source dataset
uspto-grants-1997_01
Patent number
US05597824

Reaction notes

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