Nitrite → 3-(2,3,5-Tri-O-benzoyl-beta-D-Ribofuranosyl)thiazolo[4,5-d] pyrimidine-2,7(6H)-dione

HRID 2248932Notes

Reaction equation

HRID 2248932 reaction equation
N[C:2]1[NH:3][C:4](=[O:45])[C:5]2[S:10][C:9](=[O:11])[N:8]([C@@H:12]3[O:34][C@H:33]([CH2:35][O:36][C:37](=[O:44])[C:38]4[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=4)[C@@H:23]([O:24][C:25](=[O:32])[C:26]4[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=4)[C@H:13]3[O:14][C:15](=[O:22])[C:16]3[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=3)[C:6]=2[N:7]=1.N(OC(C)(C)C)=O.N([O-])=O>C1COCC1>[C:15]([O:14][C@@H:13]1[C@H:23]([O:24][C:25](=[O:32])[C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[C@@H:33]([CH2:35][O:36][C:37](=[O:44])[C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)[O:34][C@H:12]1[N:8]1[C:6]2[N:7]=[CH:2][NH:3][C:4](=[O:45])[C:5]=2[S:10][C:9]1=[O:11])(=[O:22])[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1

Participants

5

Reactant 3

HCID 946NitriteHCID 10906Tert-Butyl nitriteHCID 1360537475-amino-3-(2,3,5-tri-O-benzoyl-beta-D-ribofuranosyl)thiazolo-[4,5-d]pyrimidine-2,7(6H)-dione

Product 1

HCID 1359816843-(2,3,5-Tri-O-benzoyl-beta-D-Ribofuranosyl)thiazolo[4,5-d] pyrimidine-2,7(6H)-dioneYield 53%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 6 (6.65 g, 10.6 mmol) in dry THF (350 mL) was added ter-butyl nitrite (6.2 mL, 52.3 mmol) and the mixture was stirred at room temperature for 1 h. Additional nitrite reagent (2.0 mL) was added and the mixture was stirred at 50°-60° C. overnight. The mixture was evaporated and the residue was purified by flash column chromatography on silica gel using 8-10% acetone in CH2Cl2 followed by 10-11%. The desired product eluted last to yield 3.45 g (46%) of 9 as a foam: UV λmax (EtOH) 220 nm (ε 46600), 259 sh (11000), 271 sh (8400): 1H NMR (DMSO-d6) δ 6.31 (d, J=6.45 Hz, 1H, C1, H), 7.38-7.98 (m, 15H, benzoyl aromatics), 8.25 (s, 1H, C5H), 13.16 (b, 1H, N6H, exchanged with D2O), and other sugar protons.

Workup

  1. stirringthe mixture was stirred at 50°-60° C. overnight
  2. customThe mixture was evaporated
  3. customthe residue was purified by flash column chromatography on silica gel using 8-10% acetone in CH2Cl2
  4. washThe desired product eluted last

Sources & evidence

ORD record
ord-e7fd949dc8ea4ee4b5c6f19ee601ecc2
Source dataset
uspto-grants-1991_08
Patent number
US05041426

Reaction notes

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