Sodium Methoxide → 2'-Deoxyimmunosine

HRID 2248943Notes

Reaction equation

HRID 2248943 reaction equation
C[O-].[Na+].[NH2:4][C:5]1[NH:6][C:7](=[O:41])[C:8]2[S:13][C:12](=[O:14])[N:11]([C@@H:15]3[O:29][C@H:28]([CH2:30][O:31]C(C4C=CC(C)=CC=4)=O)[C@@H:17]([O:18]C(C4C=CC(C)=CC=4)=O)[CH2:16]3)[C:9]=2[N:10]=1>CO>[NH2:4][C:5]1[NH:6][C:7](=[O:41])[C:8]2[S:13][C:12](=[O:14])[N:11]([C@@H:15]3[O:29][C@H:28]([CH2:30][OH:31])[C@@H:17]([OH:18])[CH2:16]3)[C:9]=2[N:10]=1

Participants

4

Reactant 2

HCID 10942334Sodium MethoxideHCID 1364426385-Amino-3-(2-deoxy-3,5-di-O-(p-toluoyl)-beta-D-erythropentofuranosyl)thiazolo[4,5-d]pyrimidin-2,7-dione

Product 1

HCID 1354611902'-Deoxyimmunosine

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

Sodium methoxide (120 mg, 2.2 mmol) was added to a solution of 5-Amino-3-(2-deoxy-3,5-di-O-(p-toluoyl)-β-D-erythropentofuranosyl)thiazolo[4,5-d]pyrimidin-2,7-dione (35; 0.465g, 0.87 mmol) in anhydrous methanol (100 mL) and the resulting solution stirred at room temperature for 8 hours. The solution was neutralized with Dowex 50W-X8 (H+ form) resin, filtered, and evaporated to dryness and the residue treated with anhydrous ether (35 mL). After trituration, the suspension was decanted to give a dry powder which was crystallized (charcoal treatment, Norit A) from ethanol. After filtering off the initial precipitate, 110 mg (42%) of the β isomer could be recovered by fractional crystallization using ethanol. mp>170° C. (scinters), UV 1H NMR (Me2SO-d6) σ4.68 (t, 1, J=5.7 Hz, C3 'OH, exchanged with D2O), 5.20 (d, 1, J=3.9 Hz, C5 'OH, exchanged with D2O), 6.24 (t, 1, J=7.2 Hz C1 'H), 6.94 (bs, 2, NH2, exchanged with D2O), 11.23 (bs, 1, N6H, exchanged with D2O); Anal. Calcd. for C10H12N4O5S: C, 40.00; H, 4.03; N, 18.66; S, 10.68; Found: C, 40.27; H, 3.92; N, 18.75; S, 10.42.

Workup

  1. filtrationfiltered
  2. customevaporated to dryness
  3. additionthe residue treated with anhydrous ether (35 mL)
  4. customAfter trituration, the suspension was decanted
  5. customto give a dry powder which
  6. customwas crystallized (charcoal treatment, Norit A) from ethanol
  7. filtrationAfter filtering off the initial precipitate, 110 mg (42%) of the β isomer
  8. customcould be recovered by fractional crystallization

Sources & evidence

ORD record
ord-e38a83306b5d4dcfaf147efa4daf03d8
Source dataset
uspto-grants-1991_08
Patent number
US05041426

Reaction notes

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