Hydrochloric Acid → HCID 89904800, compound

HRID 1746816Notes

Reaction equation

HRID 1746816 reaction equation
C([O:4][C@H:5]1[C@H:9]([CH2:10]/[CH:11]=[CH:12]\[CH2:13][CH2:14][CH2:15][C:16]([O:18]C)=[O:17])[C@@H:8]([CH2:20][O:21][Si:22]([CH3:28])([CH3:27])[C:23]([CH3:26])([CH3:25])[CH3:24])[C@H:7]([O:29][CH:30]2[CH2:35][CH2:34][CH2:33][CH2:32][O:31]2)[CH2:6]1)(=O)C.[OH-].[Na+].Cl.C(=O)([O-])O.[Na+].[I:44]I.S([O-])([O-])(=O)=S.[Na+].[Na+]>C(OCC)(=O)C.O1CCCC1>[CH3:27][Si:22]([CH3:28])([C:23]([CH3:24])([CH3:26])[CH3:25])[O:21][CH2:20][C@H:8]1[C@H:7]([O:29][CH:30]2[CH2:35][CH2:34][CH2:33][CH2:32][O:31]2)[CH2:6][C@@H:5]([OH:4])[C@@H:9]1[CH2:10][CH:11]([C@H:12]1[O:17][C:16](=[O:18])[CH2:15][CH2:14][CH2:13]1)[I:44]

Participants

9

Reactant 6

HCID 313Hydrochloric AcidHCID 807Iodine3×HCID 14798Sodium HydroxideHCID 24477Sodium ThiosulfateHCID 516892Sodium BicarbonateHCID 86702582HCID 86702582, compound

Product 1

HCID 89904800HCID 89904800, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a tetrahydrofuran (140 mL) solution of the compound 4 (34.9 g) was added a 2M aqueous sodium hydroxide solution (140 mL), and the mixture was stirred at room temperature for 18 hours and then at 50° C. for 3 hours. The mixture was cooled to −4° C. in an ice-methanol bath, and to the reaction mixture was then added dropwise 2 M hydrochloric acid (111 mL) over 12 minutes while the mixture was kept at 2° C. or lower (pH 5 to 6). The cooling bath was changed to an ice bath, and to the reaction mixture were added sodium hydrogen carbonate (28.5 g) and iodine (17.5 g), and the mixture was stirred. After 2 hours, iodine (34.2 g) was added, the mixture was further stirred for 2.5 hours, and a 5% aqueous sodium thiosulfate solution (1380 mL) was then added. When the color of iodine mostly disappeared, ethyl acetate (600 mL) was added, the mixture was stirred, and the two layers were separated. The organic layer was washed with water (150 mL) and a saturated saline (150 mL), dried with anhydrous sodium sulfate, and concentrated. The resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate=1:1→5:6) to obtain titled compounds having the following physical property values (low polar compound 8.0 g; high polar compound 20.8 g).

Workup

  1. waitat 50° C. for 3 hours
  2. temperatureThe mixture was cooled to −4° C. in an ice-methanol bath
  3. customwas kept at 2° C.
  4. customThe cooling bath was changed to an ice bath
  5. stirringthe mixture was stirred
  6. waitAfter 2 hours
  7. stirringthe mixture was further stirred for 2.5 hours
  8. stirringthe mixture was stirred
  9. customthe two layers were separated
  10. washThe organic layer was washed with water (150 mL)
  11. dry with materiala saturated saline (150 mL), dried with anhydrous sodium sulfate
  12. concentrationconcentrated
  13. customThe resulting residue was purified by silica gel column chromatography (hexane:ethyl acetate=1:1→5:6)
  14. customto obtain titled compounds

Sources & evidence

ORD record
ord-baca878ea38246fd9a8c1f15f4120eaf
Source dataset
uspto-grants-2015_10
Patent number
US09150537B2

Reaction notes

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