Dichloroacetic Acid → HCID 18633467, compound

HRID 232377Notes

Reaction equation

HRID 232377 reaction equation
ClC(Cl)C(O)=O.[C:7]([O:10][C@@H:11]1[C@@H:15]([CH3:16])[O:14][C@@H:13]([N:17]2[CH:24]=[C:23]([CH2:25][CH3:26])[C:21](=[O:22])[NH:20][C:18]2=[O:19])[CH2:12]1)(=[O:9])[CH3:8].C1(N=C=NC2CCCCC2)CCCCC1.[C:42]([CH:47]=P(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)([O:44][CH2:45][CH3:46])=[O:43]>CS(C)=O.N1C=CC=CC=1>[C:7]([O:10][C@@H:11]1[C@@H:15](/[CH:16]=[CH:47]/[C:42]([O:44][CH2:45][CH3:46])=[O:43])[O:14][C@@H:13]([N:17]2[CH:24]=[C:23]([CH2:25][CH3:26])[C:21](=[O:22])[NH:20][C:18]2=[O:19])[CH2:12]1)(=[O:9])[CH3:8]

Participants

7

Reactant 4

HCID 6597Dichloroacetic AcidHCID 10868DicyclohexylcarbodiimideHCID 70670Acetic acid, 2-(triphenylphosphoranylidene)-, ethyl esterHCID 18633449HCID 18633449, compound

Product 1

HCID 18633467HCID 18633467, compoundYield 66.1%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 1049PyridineSolvent

Procedure

1.9 g of dichloroacetic acid were added to a mixture of 8.95 g of 3'-O-acetyl-2',5'-dideoxy-5-ethyluridine and 18.6 g of dicyclohexylcarbodiimide in 75 ml of dimethyl sulfoxide. The mixture was stirred at room temperature for 24 hours. 1.2 ml of pyridine and 10.5 g of carbethoxymethylenetriphenylphosphorane were added and the mixture was stirred at room temperature for an additional 24 hours. The solvent was removed in vacuo and the residue was dissolved in 300 ml of ethyl acetate. The solution was washed with 300 ml of water, dried over anhydrous sodium sulfate and evaporated to give a yellow oil. This oil was subjected to flash chromatography on a column of silica gel using 5% methanol/dichloromethane for the elution. The product was recrystallized from ethanol to give 7.3 g of trans-3'-O-acetyl-2',5'-dideoxy-5'-(ethoxycarbonylmethylene)-5-ethyluridine in the form of a white solid of melting point 132°-133° C.

Workup

  1. stirringthe mixture was stirred at room temperature for an additional 24 hours
  2. customThe solvent was removed in vacuo
  3. dissolutionthe residue was dissolved in 300 ml of ethyl acetate
  4. washThe solution was washed with 300 ml of water
  5. dry with materialdried over anhydrous sodium sulfate
  6. customevaporated
  7. customto give a yellow oil
  8. washThis oil was subjected to flash chromatography on a column of silica gel using 5% methanol/dichloromethane for the elution
  9. customThe product was recrystallized from ethanol

Sources & evidence

ORD record
ord-5f64adfdebe5474cbf6aa2e6d1b5b09a
Source dataset
uspto-grants-1989_07
Patent number
US04851519

Reaction notes

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