Methanol → 2-Thioadenosine

HRID 1729613Notes

Reaction equation

HRID 1729613 reaction equation
[C@@H:1]1([N:10]2[C:19]3[C:13](=[C:14]([N+:16]([O-])=[CH:17][N:18]=3)[NH2:15])[N:12]=[CH:11]2)[O:9][C@H:6]([CH2:7][OH:8])[C@@H:4]([OH:5])[C@H:2]1[OH:3].[OH-].[Na+].CO.C(=S)=[S:26]>>[CH:11]1[N:10]([C@@H:1]2[O:9][C@H:6]([CH2:7][OH:8])[C@@H:4]([OH:5])[C@H:2]2[OH:3])[C:19]2[C:13](=[C:14]([NH2:15])[NH:16][C:17]([N:18]=2)=[S:26])[N:12]=1

Participants

5

Reactant 4

HCID 887MethanolHCID 6348Carbon DisulfideHCID 14798Sodium HydroxideHCID 178507181HCID 178507181, compound

Product 1

HCID 64519652-ThioadenosineYield 92%

Procedure

8.0 g of adenosine 1-oxide (26.67 mmol) was refluxed in 75 ml of a 5N sodium hydroxide aqueous solution for 15 minutes. The resulting liquid was neutralized to a pH of 5.0 with Amberlite IRC-50 (H+-type) and concentrated to a small volume to prepare 1-β-D-ribofuranosyl-5-aminoimidazole-4-carboxamide oxime. To this was added 200 ml of an aqueous solution containing 175 ml of methanol, the resulting solution being found to have a pH of 9. 50 ml of carbon disulfide was added to the solution, and the mixture was allowed to react in an autoclave at 120° C for 5 hours under autogenous pressure (about 10 Kg/cm2). The orange colored substance formed was removed and concentrated to dryness. The residue was dissolved in 63 ml of 2.5N aqueous ammonia, and any impurities were filtered out. A mixture of n-butanol and acetic acid (125 ml: 63 ml) was added to the filtrate to crystallize the product to obtain 5.42 g of 2-thioadenosine having a melting point of 199° C (with decomposition) in a 92% yield.

Workup

  1. concentrationconcentrated to a small volume
  2. customto prepare 1-β-D-ribofuranosyl-5-aminoimidazole-4-carboxamide oxime
  3. customto react in an autoclave at 120° C for 5 hours under autogenous pressure (about 10 Kg/cm2)
  4. customThe orange colored substance formed
  5. customwas removed
  6. concentrationconcentrated to dryness
  7. dissolutionThe residue was dissolved in 63 ml of 2.5N aqueous ammonia
  8. filtrationany impurities were filtered out
  9. additionA mixture of n-butanol and acetic acid (125 ml: 63 ml)
  10. additionwas added to the filtrate
  11. customto crystallize the product

Sources & evidence

ORD record
ord-e52911cd1bff47f2a8d5496c3fd8289f
Source dataset
uspto-grants-1976_11
Patent number
US03989682

Reaction notes

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