Tin tetrachloride → HCID 58786117, compound

HRID 1375983Notes

Reaction equation

HRID 1375983 reaction equation
[Sn](Cl)(Cl)(Cl)Cl.C(O[C@@H:10]1[O:27][C@H:26]([CH2:28][O:29][C:30](=[O:32])[CH3:31])[C@@H:21]([O:22][C:23](=[O:25])[CH3:24])[C@H:16]([O:17][C:18](=[O:20])[CH3:19])[C@H:11]1[O:12][C:13](=[O:15])[CH3:14])(=O)C.[CH2:33]([O:35][C:36]1[CH:41]=[CH:40][C:39]([CH3:42])=[CH:38][C:37]=1[O:43][CH2:44][CH3:45])[CH3:34].C(=O)(O)[O-].[Na+]>ClCCCl.FC(F)(F)C([O-])=O.[Ag+].ClCCl>[C:13]([O:12][C@@H:11]1[C@@H:16]([O:17][C:18](=[O:20])[CH3:19])[C@H:21]([O:22][C:23](=[O:25])[CH3:24])[C@@H:26]([CH2:28][O:29][C:30](=[O:32])[CH3:31])[O:27][C@H:10]1[C:41]1[CH:40]=[C:39]([CH3:42])[CH:38]=[C:37]([O:43][CH2:44][CH3:45])[C:36]=1[O:35][CH2:33][CH3:34])(=[O:15])[CH3:14]

Participants

8

Reactant 4

HCID 24287Tin tetrachlorideHCID 757883,4-DiethoxytolueneHCID 516892Sodium BicarbonateHCID 2724702beta-D-Glucose pentaacetate

Product 1

HCID 58786117HCID 58786117, compoundYield 35.9%

Reagents, catalysts & solvents 3

HCID 76299Silver trifluoroacetateCatalystHCID 111,2-DichloroethaneSolventHCID 6344DichloromethaneSolvent

Procedure

A 1.0 M dichloromethane solution of tin tetrachloride (16.5 ml) was added to a suspension of 1,2,3,4,6-penta-O-acetyl-β-D-glucopyranose (6.41 g), 1,2-diethoxy-4-methylbenzene (2.47 g), and silver trifluoroacetate (3.63 g) in 1,2-dichloroethane (70 ml) at 0° C. and the mixture was stirred at the same temperature for one hour. After heating to room temperature and stirring for 15 hours, saturated aqueous solution of sodium bicarbonate was added to the mixture. The reaction mixture was filtered through celite and the filtrate was extracted with chloroform. The organic layer was washed with water and saturated brine and dried over anhydrous sodium sulfate. After filtration, the solvent was evaporated under reduced pressure. Methanol (200 ml) and a catalytic amount of sodium methoxide were added to the resulting residue and the mixture was stirred at room temperature overnight. The solvent was evaporated under reduced pressure and the resulting residue was purified by silica gel column chromatography (chloroform-methanol). Pyridine (30 ml), acetic anhydride (5 ml), and a catalytic amount of 4-dimethylaminopyridine were added to the resulting residue and the mixture was stirred at room temperature for two days. Toluene was added to the reaction mixture and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate-n-hexane) to obtain (1S)-2,3,4,6-tetra-O-acetyl-1,5-anhydro-1-(2,3-diethoxy-5-methylphenyl)-D-glucitol (2.51 g).

Workup

  1. stirringstirring for 15 hours
  2. filtrationThe reaction mixture was filtered through celite
  3. extractionthe filtrate was extracted with chloroform
  4. washThe organic layer was washed with water and saturated brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. filtrationAfter filtration
  7. customthe solvent was evaporated under reduced pressure
  8. additionMethanol (200 ml) and a catalytic amount of sodium methoxide were added to the resulting residue
  9. stirringthe mixture was stirred at room temperature overnight
  10. customThe solvent was evaporated under reduced pressure
  11. customthe resulting residue was purified by silica gel column chromatography (chloroform-methanol)
  12. additionPyridine (30 ml), acetic anhydride (5 ml), and a catalytic amount of 4-dimethylaminopyridine were added to the resulting residue
  13. stirringthe mixture was stirred at room temperature for two days
  14. additionToluene was added to the reaction mixture
  15. customthe solvent was evaporated under reduced pressure
  16. customThe residue was purified by silica gel column chromatography (ethyl acetate-n-hexane)

Sources & evidence

ORD record
ord-4d38d981811d4c03962d4a55529cd1b1
Source dataset
uspto-grants-2007_01
Patent number
US07169761B2

Reaction notes

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