Bis(p-nitrophenyl)-phosphate → 5,7-Dichloro-3-(2,3,5-tri-O-acetyl-beta-D-ribofuranosyl)thiazolo[4,5-d]pyrimidin-2-one

HRID 1638532Notes

Reaction equation

HRID 1638532 reaction equation
[Cl:1][C:2]1[N:3]=[C:4]([Cl:12])[C:5]2[S:10][C:9](=[O:11])[NH:8][C:6]=2[N:7]=1.C(O[CH:17]1[O:29][C@H:28]([CH2:30][O:31][C:32](=[O:34])[CH3:33])[C@@H:23]([O:24][C:25](=[O:27])[CH3:26])[C@H:18]1[O:19][C:20](=[O:22])[CH3:21])(=O)C.[N+](C1C=CC(OP([O-])(OC2C=CC([N+]([O-])=O)=CC=2)=O)=CC=1)([O-])=O>CCOC(C)=O>[Cl:1][C:2]1[N:3]=[C:4]([Cl:12])[C:5]2[S:10][C:9](=[O:11])[N:8]([C@@H:17]3[O:29][C@H:28]([CH2:30][O:31][C:32](=[O:34])[CH3:33])[C@@H:23]([O:24][C:25](=[O:27])[CH3:26])[C@H:18]3[O:19][C:20](=[O:22])[CH3:21])[C:6]=2[N:7]=1

Participants

5

Reactant 3

HCID 5255575Bis(p-nitrophenyl)-phosphateHCID 9797055D-Ribofuranose, 1,2,3,5-tetraacetateHCID 145057565,7-Dichlorothiazolo[4,5-d]pyrimidin-2(3H)-one

Product 1

HCID 539710355,7-Dichloro-3-(2,3,5-tri-O-acetyl-beta-D-ribofuranosyl)thiazolo[4,5-d]pyrimidin-2-one

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
170 °C

Procedure

A finely powdered mixture of 24 (3.7 g, 16 mmol), 1,2,3,5-tetra-O-acetyl-D-ribofuranose (5.3 g, 16 mmol) and bis(p-nitrophenyl)phosphate (20 mg) was heated at 170° C. for 10 min under reduced pressure. After cooling to room temperature the brown solid mass was dissolved in EtOAc (500 mL) and washed with saturated aqueous sodium bicarbonate (3×300 mL). The dried (Na2SO4) organic layer was evaporated to yield a syrup which was purified by silica gel column chromatography (4×40 cm) using toluene-EtOAc (5:1). The resulting syrup was crystallized from ethanol to give a colorless powder: yield 6.4 g, 80%: mp 125°-126° C.: 1H NMR (DMSO-d6) δ1.99, 2.06, 2.08 (3s, 9H, acetyl), 6.07 (d, J=3.40 Hz, 1H, C1,H), and other sugar protons. Anal. Calcd. for C16H15Cl2N3O8S: C, 40.01: H, 3.15: Cl, 14.76: N, 8.75: S, 6.68. Found: C, 40.20: H, 3.31: Cl, 14.79: N, 8.61: S, 6.66.

Workup

  1. temperatureAfter cooling to room temperature the brown solid mass
  2. washwashed with saturated aqueous sodium bicarbonate (3×300 mL)
  3. dry with materialThe dried (Na2SO4) organic layer
  4. customwas evaporated
  5. customto yield a syrup which
  6. customwas purified by silica gel column chromatography (4×40 cm)
  7. customThe resulting syrup was crystallized from ethanol
  8. customto give a colorless powder

Sources & evidence

ORD record
ord-4922f1469d0a446aa33d8504f8bf75e2
Source dataset
uspto-grants-1989_11
Patent number
US04880784

Reaction notes

Loading…