Pyridine → HCID 11092045, compound

HRID 1199118Notes

Reaction equation

HRID 1199118 reaction equation
[H-].[Na+].[CH2:3](Br)[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.[C:11]([O:30][CH2:31][C@H:32]1[O:38][CH:35]([O:36][CH3:37])[CH2:34][C@@H:33]1[OH:39])([C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)([C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.N1C=CC=CC=1>O1CCCC1>[CH2:3]([O:39][C@@H:33]1[C@@H:32]([CH2:31][O:30][C:11]([C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)([C:12]2[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=2)[C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[O:38][CH:35]([O:36][CH3:37])[CH2:34]1)[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1

Participants

6

Reactant 4

HCID 1049PyridineHCID 7498Benzyl Bromide2×HCID 24758Sodium hydrideHCID 13912247Methyl 2-deoxy-5-O-(triphenylmethyl)-D-erythro-pentofuranoside

Product 1

HCID 11092045HCID 11092045, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a stirred mixture of 1.3 g (0.054 mole) of sodium hydride, 10.8 g (7.5 ml, 0.063 mole) of benzyl bromide and 50 ml dry tetrahydrofuran or other aprotic solvent under a dry nitrogen atmosphere were added slowly a solution of 14.8 g (0.038 mole) of crude methyl 2-deoxy-5-O-tritylribofuranoside in 100 ml of dry tetrahydrofuran. After the addition was completed (0.5 hr), the mixture was stirred at ambient temperature for 4 hrs., then at 65°-70° C. for an additional 2 hrs. The mixture was cooled, vacuum filtered through filter-aid, then heated at reflux for 2 hrs. with 15 ml (0.2 mole) of pyridine to consume the excess benzyl bromide. The mixture was again cooled and vacuum filtered through filter-aid. The solvent was removed from the filtrate under reduced pressure. Toluene (2×150 ml) was then added and evaporated. The residue (24.3 g.) was taken up in ethyl acetate (200 ml), washed with saturated NaCl solution (150 ml), then with DI water (150 ml). The organic phase was dried (Na2SO4), filtered and the solvent evaporated under vacuum. The red-orange oil that remained was used directly in subsequent coupling reactions. An analytical sample was prepared by chromatography on silica gel eluting with 10% ethyl acetate in hexane. The light-yellow oil thus prepared showed the following: 1H NMR (CDCl3) δ2.05 (m, 2, CH2), 3.18 (s, 3, OCH3), 3.33 (s, 2, CH2), 3.6 to 4.4 (m, 2, OCH), 4.42 (d, 2, CH2), 4.9 to 5.1 (m, 1, anomeric CH), 7.1 to 7.7 (m, 20, ArH); IR (neat) 3090 cm-1 (w), 3060 (m), 3035 (m), 2920 (m), 1598 (w), 1490 (m), 1448 (s), 1362 (m), 1080 (s), 762 (m), 748 (m), 705 (s), 633 (m).

Workup

  1. additionAfter the addition
  2. custom(0.5 hr)
  3. wait, then at 65°-70° C. for an additional 2 hrs
  4. temperatureThe mixture was cooled
  5. filtrationvacuum filtered
  6. filtrationthrough filter-aid
  7. temperatureheated
  8. temperatureat reflux for 2 hrs
  9. temperatureThe mixture was again cooled
  10. filtrationvacuum filtered
  11. filtrationthrough filter-aid
  12. customThe solvent was removed from the filtrate under reduced pressure
  13. additionToluene (2×150 ml) was then added
  14. customevaporated
  15. washwashed with saturated NaCl solution (150 ml)
  16. dry with materialThe organic phase was dried (Na2SO4)
  17. filtrationfiltered
  18. customthe solvent evaporated under vacuum
  19. customAn analytical sample was prepared by chromatography on silica gel eluting with 10% ethyl acetate in hexane
  20. customThe light-yellow oil thus prepared

Sources & evidence

ORD record
ord-a706b3292a7f4ebd9103844294e89ebe
Source dataset
uspto-grants-1990_02
Patent number
US04898936

Reaction notes

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