Chlorotrimethylsilane → HCID 15086889, compound

HRID 1110841Notes

Reaction equation

HRID 1110841 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6]([NH:8][C:9](=[O:13])[O:10][CH2:11][CH3:12])[N:5]=[C:4]2[NH:14][CH:15]=[N:16][C:3]=12.C(O[C@@H:21]1[O:43][C@H:42]([CH2:44][O:45]C(=O)C2C=CC=CC=2)[C@@H:32]([O:33]C(=O)C2C=CC=CC=2)[C@H:22]1[O:23]C(=O)C1C=CC=CC=1)(=O)C.FC(F)(F)C(F)(F)C(F)(F)C(F)(F)S([O-])(=O)=O.[K+].C[Si](C)(C)N[Si](C)(C)C.C[Si](Cl)(C)C.C(=O)(O)[O-].[Na+]>C(#N)C.C(Cl)Cl.CO.N>[Cl:1][C:2]1[CH:7]=[C:6]([NH:8][C:9](=[O:13])[O:10][CH2:11][CH3:12])[N:5]=[C:4]2[N:14]([C@@H:21]3[O:43][C@H:42]([CH2:44][OH:45])[C@@H:32]([OH:33])[C@H:22]3[OH:23])[CH:15]=[N:16][C:3]=12

Participants

11

Reactant 6

HCID 6397ChlorotrimethylsilaneHCID 13838HexamethyldisilazaneHCID 81455beta-D-Ribofuranose, 1-acetate 2,3,5-tribenzoateHCID 516892Sodium BicarbonateHCID 23675274Potassium perfluorobutanesulfonateHCID 178473434HCID 178473434, compound

Product 1

HCID 15086889HCID 15086889, compound

Reagents, catalysts & solvents 4

HCID 222AmmoniaSolventHCID 887MethanolSolventHCID 6342AcetonitrileSolvent2×HCID 6344DichloromethaneSolvent

Procedure

To a mixture of 1.2 g ethyl N-(7-chloro-3H-imidazo-[4,5-b]-pyridin-5-yl)-carbamate, prepared as described by Schelling and Salemink, Receuil 93 (6), 160 (1974), 2.52 g of 1-O-acetyl-2,3,5-tri-O-benzoyl-β-D-ribofuranose, 4.06 g potassium nonafluorobutanesulfonate and 0.56 g hexamethyldisilazane in 70 ml of acetonitrile is added 1.67 g of trimethylsilyl chloride. The mixture is heated to reflux under nitrogen for 21 hours. It is cooled, diluted with methylene chloride (100 ml) and treated with saturated aqueous sodium bicarbonate (50 ml). The organic phase is separated, and the aqueous layer is extracted with methylene chloride. The combined organic layers are washed with saturated aqueous sodium bicarbonate, then with brine, and then dried (sodium sulfate). Evaporation of the solvent in vacuo gives an oil which is dissolved in 100 ml of methanol saturated with ammonia, and the solution is stirred at room temperature for 40 hours. The clear solution is concentrated in vacuo, the residue is redissolved in water and washed twice with ether. The aqueous layer is concentrated in vacuo to give a glass. It is dissolved in hot acetonitrile, the solution is filtered, and the solvent is evaporated in vacuo to afford ethyl N-[7-chloro-3-β-D-ribofuranosyl-3H-imidazo[4,5-b]pyridin-5-yl]-carbamate, m.p 107°-111°.

Workup

  1. customprepared
  2. temperatureThe mixture is heated
  3. temperatureto reflux under nitrogen for 21 hours
  4. temperatureIt is cooled
  5. customThe organic phase is separated
  6. extractionthe aqueous layer is extracted with methylene chloride
  7. washThe combined organic layers are washed with saturated aqueous sodium bicarbonate
  8. dry with materialwith brine, and then dried (sodium sulfate)
  9. customEvaporation of the solvent in vacuo
  10. customgives an oil which
  11. concentrationThe clear solution is concentrated in vacuo
  12. dissolutionthe residue is redissolved in water
  13. washwashed twice with ether
  14. concentrationThe aqueous layer is concentrated in vacuo
  15. customto give a glass
  16. filtrationthe solution is filtered
  17. customthe solvent is evaporated in vacuo

Sources & evidence

ORD record
ord-a7ee7aa465d84529af900e7f12692c42
Source dataset
uspto-grants-1990_12
Patent number
US04977144

Reaction notes

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