Toluene → HCID 25241750, compound

HRID 907041Notes

Reaction equation

HRID 907041 reaction equation
C1(C)C=CC=CC=1.[I:8][C:9]1[CH:10]=[C:11]([OH:15])[CH:12]=[CH:13][CH:14]=1.C(N(CC)CC)C.[C:23]([O:26][C@@H:27]1[C@@H:32]([O:33][C:34](=[O:36])[CH3:35])[C@H:31]([O:37][C:38](=[O:40])[CH3:39])[CH2:30][S:29][C@@H:28]1Br)(=[O:25])[CH3:24]>[Cl-].[Zn+2].[Cl-].C(OCC)(=O)C.O.C(#N)C>[C:23]([O:26][C@@H:27]1[C@@H:32]([O:33][C:34](=[O:36])[CH3:35])[C@H:31]([O:37][C:38](=[O:40])[CH3:39])[CH2:30][S:29][C@H:28]1[O:15][C:11]1[CH:12]=[CH:13][CH:14]=[C:9]([I:8])[CH:10]=1)(=[O:25])[CH3:24]

Participants

9

Reactant 4

HCID 1140TolueneHCID 8471TriethylamineHCID 122723-IodophenolHCID 109263142,3,4-tri-O-acetyl-5-thio-alpha-xylopyranosyl bromide

Product 1

HCID 25241750HCID 25241750, compoundYield 37%

Reagents, catalysts & solvents 4

HCID 3007855ZincchlorideCatalystHCID 962WaterSolventHCID 6342AcetonitrileSolventHCID 8857Ethyl AcetateSolvent

Procedure

38.63 g (0.28 mol) of zinc chloride are heated until molten under an argon atmosphere in a reactor. After cooling the reaction mass, 800 ml of toluene, 800 ml of acetonitrile and 44 g of 4 Å molecular sieve are added. The reaction mixture is stirred at ambient temperature for 90 minutes and 25 g (0.113 mol) of 3-iodophenol are added. The reaction mixture is brought to 90° C. and, after 2 minutes, 39 ml (0.28 mol) of triethylamine and 44.39 g (0.12 mol) of 2,3,4-tri-O-acetyl-5-thio-α-D-xylopyranosyl bromide are added. The reaction mixture is kept stirred at 80° C. for 30 minutes. After cooling, water and ethyl acetate are added and the insoluble compounds are removed by filtration. The organic phase is washed successively with water, a 1N sodium hydroxide solution and a saturated sodium chloride solution. The organic phase is dried over magnesium sulfate, decolored using active charcoal, filtered and evaporated under reduced pressure. The residue is purified by chromatography on a silica column, elution being carried out using a cyclohexane/ethyl acetate mixture (70/30; v/v), and recrystallized from isopropanol. The expected product is obtained in the form of a white powder with a yield of 37%.

Workup

  1. customuntil molten under an argon atmosphere in a reactor
  2. additionare added
  3. waitThe reaction mixture is brought to 90° C. and, after 2 minutes
  4. stirringThe reaction mixture is kept stirred at 80° C. for 30 minutes
  5. temperatureAfter cooling
  6. customthe insoluble compounds are removed by filtration
  7. washThe organic phase is washed successively with water
  8. dry with materialThe organic phase is dried over magnesium sulfate
  9. filtrationfiltered
  10. customevaporated under reduced pressure
  11. customThe residue is purified by chromatography on a silica column, elution
  12. customrecrystallized from isopropanol

Sources & evidence

ORD record
ord-9077a47a467b4ea58b4b0642d98b64e7
Source dataset
uspto-grants-2011_09
Patent number
US08013010B2

Reaction notes

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