Sodium Dithionite → HCID 54249281, compound

HRID 1814935Notes

Reaction equation

HRID 1814935 reaction equation
[C:1]([O:4][C@H:5]([CH3:20])[CH2:6][CH2:7][CH2:8][CH2:9][N:10]1[C:15](=[O:16])[CH:14]=[C:13]([NH2:17])[N:12]([CH3:18])[C:11]1=[O:19])(=[O:3])[CH3:2].[N:21]([O-])=O.[Na+].S(S([O-])=O)([O-])=O.[Na+].[Na+]>C(O)(=O)C.O>[C:1]([O:4][C@H:5]([CH3:20])[CH2:6][CH2:7][CH2:8][CH2:9][N:10]1[C:15](=[O:16])[C:14]([NH2:21])=[C:13]([NH2:17])[N:12]([CH3:18])[C:11]1=[O:19])(=[O:3])[CH3:2]

Participants

6

Reactant 3

HCID 24489Sodium DithioniteHCID 23668193Sodium NitriteHCID 54017983HCID 54017983, compound

Product 1

HCID 54249281HCID 54249281, compound

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 962WaterSolvent

Conditions

Temperature
65 °C

Procedure

To the stirring solution of (R)-3-(5-acetoxyhexyl)-6-amino-1-methyluracil (1.13 g, 4.0 mmol) in glacial acetic acid (22.5 ml) and water (7.5 ml) at 65° C. was added sodium nitrite (345 mg, 5.0 mmol) in portions. The pink mixture was stirred at 65° C. for 1 hour and then cooled to 0-5° C. After filtration, the violet solid was washed with water (2x 10 ml) and then suspended in water (20 ml) and heated at 65° C. while sodium hydrosulfite (2.78 g, 16.0 mmol) was added in portions. The pale yellow solution was stirred at 65° C. for an additional 1 hour, cooled to room temperature and extracted with chloroform (3x 25 ml). The combined extracts were dried over magnesium sulfate and filtered to provide crude (R)-3-(5-acetoxyhexyl)-5,6-diamino-1-methyluracil in chloroform. To this clear solution was added 1,1′-carbonyldiimidazole (650 mg, 4.0 mmol). After stirring overnight at room temperature, the mixture was washed with water (2x 25 ml), with 1 N aqueous hydrochloric add (2x 25 ml), with water (2x 25 ml), with saturated aqueous sodium chloride solution (25 ml) and then dried over magnesium sulfate. Evaporation of the solvent under reduced pressure provided the crude product which was purified by flash chromatography on silica gel eluting with ethyl acetate to provide (R)-1-(5-acetoxyhexyl)-3-methyluric acid (280 mg) as a beige solid which was dissolved in 20 ml of ethanol. To this solution was added hydrogen chloride in ethyl ether (1 M, 2.0 ml, 2.0 mmol). After refluxing overnight, the solvent was evaporated under reduced pressure. The crude product was purified by flash chromatography on silica gel eluting with ethyl acetate-methanol (7:1) to provide (R)-1-(5-hydroxyhexyl)-3-methyluric acid (210 mg, 19% yield) as a beige solid.

Workup

  1. temperaturecooled to 0-5° C
  2. filtrationAfter filtration
  3. washthe violet solid was washed with water (2x 10 ml)
  4. additionwas added in portions
  5. stirringThe pale yellow solution was stirred at 65° C. for an additional 1 hour
  6. temperaturecooled to room temperature
  7. extractionextracted with chloroform (3x 25 ml)
  8. dry with materialThe combined extracts were dried over magnesium sulfate
  9. filtrationfiltered

Sources & evidence

ORD record
ord-2556dac6925747da8e58d121db85371d
Source dataset
uspto-grants-2005_04
Patent number
US06878715B1

Reaction notes

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