Acetone → 2-Imino-9-pentofuranosyl-3,9-dihydro-2H-purine-6-sulfinamide

HRID 1494511Notes

Reaction equation

HRID 1494511 reaction equation
[NH2:1][C:2]1[N:10]=[C:9]2[C:5]([N:6]=[CH:7][N:8]2[C@@H:11]2[O:17][C@H:16]([CH2:18][OH:19])[C@@H:14]([OH:15])[C@H:12]2[OH:13])=[C:4]([S:20][NH2:21])[N:3]=1.O.CC(C)=[O:25].ClC1C=C(C=CC=1)C(OO)=O>C(O)C>[NH2:1][C:2]1[N:10]=[C:9]2[C:5]([N:6]=[CH:7][N:8]2[C@@H:11]2[O:17][C@H:16]([CH2:18][OH:19])[C@@H:14]([OH:15])[C@H:12]2[OH:13])=[C:4]([S:20]([NH2:21])=[O:25])[N:3]=1

Participants

6

Reactant 4

HCID 180AcetoneHCID 962WaterHCID 70297m-Chloroperbenzoic acidHCID 1298626-(Aminosulfanyl)-9-pentofuranosyl-3,9-dihydro-2H-purin-2-imine

Product 1

HCID 1302092-Imino-9-pentofuranosyl-3,9-dihydro-2H-purine-6-sulfinamide

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent2×

Procedure

A mixture of 2-amino-9-β-D-ribofuranosyl-9H-purine-6-sulfenamide (18) (1.57 g, 0.005 mol), ethanol (700 mL) and water (50 mL) was vigorously stirred and cooled in an ice bath. After the temperature of the suspension had decreased to <10° C., acetone was added to the ice bath to obtain a temperature of <0° C. With continual stirring a solution of commercially available (Aldrich Chem Co.) 3-chloroperoxybenzoic acid (80-85%, 1.0 g, 0.0046-0.0049 mol) in ethanol (40 mL) was added dropwise over a period of approx. 15 min. The reaction flask was stoppered, the mixture was allowed to stir and warm as the ice melted, and then stirred at ambient temperature for a total reaction time of 19 hr. The reaction mixture was filtered (Whatman GF/A glass microfiber filter) to remove a trace of undissolved solid and then the filtrate was evaporated in vacuo and at a temperature of >25° C. to near dryness. The product was washed from the evaporation flask with acetone (50-100 mL) and the solid was collected by filtration, suspended in diethyl ether (50 mL), refiltered, dried under vacuum at ambient temperature: (1.3 g, 0.0042 mol, 85%), m.p. 183°-185° C. dec. with prior sintering and darkening. IR (KBr): 1040 (vs, S=O), 3000-3600 (NH2, OH)cm-1 : UV: λmax (pH 1) 333 nm (ε2,900): λmax (pH 7) 326 nm (ε10,700): λmax (pH 11) 325 nm (ε8,700): 1H NMR (DMSO-d6): δ 5.85 (d, 1, J =5.52 Hz, C1'H), 6.49 (s, 2, SONH2, exchanged with D2O), 6.98 (s, 2, NH2, exchanged with D2O), 8.45 (s, 1, C8 e,uns/H/ ), and other sugar protons. Anal. Calcd. for C10H14N6O5S.1/2C2H5OH (353.32): C, 37.39: H, 4.82: N, 23.80: S, 9.07. Found: C, 37.29: H, 4.56: N, 23.78: S, 8.92.

Workup

  1. temperaturecooled in an ice bath
  2. customhad decreased to <10° C.
  3. customto obtain a temperature of <0° C
  4. additionwas added dropwise over a period of approx. 15 min
  5. stirringto stir
  6. stirringstirred at ambient temperature for a total reaction time of 19 hr
  7. filtrationThe reaction mixture was filtered
  8. filtration(Whatman GF/A glass microfiber filter)
  9. customto remove a trace of undissolved solid
  10. customthe filtrate was evaporated in vacuo and at a temperature of >25° C.
  11. washThe product was washed from the evaporation flask with acetone (50-100 mL)
  12. filtrationthe solid was collected by filtration
  13. customdried under vacuum at ambient temperature

Sources & evidence

ORD record
ord-b45e53863dd244f4bf56e1c7c89053e5
Source dataset
uspto-grants-1991_06
Patent number
US05026836

Reaction notes

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