Formic Acid → HCID 88430022, compound

HRID 1089418Notes

Reaction equation

HRID 1089418 reaction equation
C(OC(=O)C)(=O)C.[CH:8]([OH:10])=O.[Si:11]([O:18][C@@H:19]1[C@H:23]([O:24][Si:25]([C:28]([CH3:31])([CH3:30])[CH3:29])([CH3:27])[CH3:26])[C@@H:22]([CH3:32])[O:21][C@H:20]1[N:33]1[CH:40]=[C:39]([F:41])[C:37]([NH2:38])=[N:36][C:34]1=[O:35])([C:14]([CH3:17])([CH3:16])[CH3:15])([CH3:13])[CH3:12]>N1C=CC=CC=1>[Si:11]([O:18][C@@H:19]1[C@H:23]([O:24][Si:25]([C:28]([CH3:30])([CH3:31])[CH3:29])([CH3:27])[CH3:26])[C@@H:22]([CH3:32])[O:21][C@H:20]1[N:33]1[CH:40]=[C:39]([F:41])[C:37]([NH:38][CH:8]=[O:10])=[N:36][C:34]1=[O:35])([C:14]([CH3:15])([CH3:16])[CH3:17])([CH3:13])[CH3:12]

Participants

5

Reactant 3

HCID 284Formic AcidHCID 7918Acetic AnhydrideHCID 18641814HCID 18641814, compound

Product 1

HCID 88430022HCID 88430022, compound

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Conditions

Temperature
50 °C

Procedure

To ice cooled acetic anhydride (0.57 ml) was added dropwise 99% formic acid (286 μl). The solution was stirred for 15 minutes at 0° C. and for 50 minutes at 50° C., and then cooled to 0° C. To the solution was added 2',3'-bis-O-(tert-butyldimethylsilyl)-5'-deoxy-5-fluorocytidine (473 mg) obtained in Reference example (a) in dry pyridine (5 ml) at 0° C. The reaction mixture was stirred for 10 minutes at 0° C. and for 26 hours at room temperature. After removal of the solvent under reduced pressure the residue was partitioned between water and ethyl acetate. The organic layer was washed with saturated sodium hydrogen carbonate solution and water, and dried over anhydrous sodium sulfate. Ethyl acetate was evaporated under reduced pressure and the residue was purified by silica gel column chromatography (n-hexane - ethyl acetate) followed by recrystallization from n-hexane - ethyl acetate to give 144 mg of 2',3'-bis-O-(tert-butyldimethylsilyl)-5 '-deoxy-5-fluoro-N4 -formylcytidine, mp 188° C. (dec.); MS 502 (MH+).

Workup

  1. temperaturecooled to 0° C
  2. stirringThe reaction mixture was stirred for 10 minutes at 0° C. and for 26 hours at room temperature
  3. customAfter removal of the solvent under reduced pressure the residue
  4. customwas partitioned between water and ethyl acetate
  5. washThe organic layer was washed with saturated sodium hydrogen carbonate solution and water
  6. dry with materialdried over anhydrous sodium sulfate
  7. customEthyl acetate was evaporated under reduced pressure
  8. customthe residue was purified by silica gel column chromatography (n-hexane - ethyl acetate)
  9. customfollowed by recrystallization from n-hexane - ethyl acetate

Sources & evidence

ORD record
ord-34ff1b9504d34d9f97eb5be36f899783
Source dataset
uspto-grants-1990_10
Patent number
US04966891

Reaction notes

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