Diethyl Ether → 2,2'-Anhydrouridine

HRID 2258413Notes

Reaction equation

HRID 2258413 reaction equation
[C@@H:1]1([N:10]2[CH:17]=[CH:16][C:14](=[O:15])[NH:13][C:11]2=[O:12])[O:9][C@H:6]([CH2:7][OH:8])[C@@H:4]([OH:5])[C@H:2]1O.C(=O)(OC1C=CC=CC=1)OC1C=CC=CC=1.C(OCC)C>CN(C)P(N(C)C)(N(C)C)=O.C(=O)(O)[O-].[Na+]>[CH:16]1[C:14](=[O:15])[N:13]=[C:11]2[N:10]([C@@H:1]3[O:9][C@H:6]([CH2:7][OH:8])[C@@H:4]([OH:5])[C@@H:2]3[O:12]2)[CH:17]=1

Participants

6

Reactant 3

HCID 3283Diethyl EtherHCID 6029UridineHCID 7597Diphenyl carbonate

Product 1

HCID 8061382,2'-AnhydrouridineYield 92%

Reagents, catalysts & solvents 2

HCID 516892Sodium BicarbonateCatalystHCID 12679HexamethylphosphoramideSolvent

Conditions

Temperature
135 °C

Procedure

To a suspension of uridine (200 g, 819 mmoles) in hexamethylphosphoramide (HMPA) (400 ml) was added sodium bicarbonate (5.3 g, 63.1 mmoles, 0.077 equivalents (eq.)) and diphenyl carbonate (228.1 g, 1064.7 mmoles, 1.3 eq.). The mixture was heated to 135° C. for 11 h. After cooling to room temperature, diethyl ether (2 l) was added and the precipitate was filtered off. The solid was washed three times with ether (3×1 l). Water (1 l) was added to the filtrate, the aqueous layer was separated and extracted three times with methylene chloride (3×l). The aqueous phase was evaporated to dryness. The combined solids were recrystallized from hot methanol to yield 170 g (92%) of 2,2'-anhydrouridine. The spectral properties agreed with those reported in the literature (Hampton and Nichol (1966) Biochemistry 5:2076).

Workup

  1. temperatureAfter cooling to room temperature
  2. filtrationthe precipitate was filtered off
  3. washThe solid was washed three times with ether (3×1 l)
  4. additionWater (1 l) was added to the filtrate
  5. customthe aqueous layer was separated
  6. extractionextracted three times with methylene chloride (3×l)
  7. customThe aqueous phase was evaporated to dryness
  8. customThe combined solids were recrystallized from hot methanol

Sources & evidence

ORD record
ord-bf7303cbe5d64617b5102457ced64d87
Source dataset
uspto-grants-1997_08
Patent number
US05660985

Reaction notes

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