Dichloromethane → HCID 66738924, compound

HRID 1641370Notes

Reaction equation

HRID 1641370 reaction equation
C([O:4][C:5]1([O:14][CH2:13][C@:11]([C:15](=[O:22])[C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)([OH:12])[C@:9]([C:23](=[O:30])[C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)([OH:10])[C@@:7]1([C:31](=[O:38])[C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1)[OH:8])O)CC.[BrH:39].C(O)(=O)C.ClCCl>O>[Br:39][C:5]1([O:14][CH2:13][C@:11]([C:15](=[O:22])[C:16]2[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=2)([OH:12])[C@:9]([C:23](=[O:30])[C:24]2[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=2)([OH:10])[C@@:7]1([C:31](=[O:38])[C:32]1[CH:33]=[CH:34][CH:35]=[CH:36][CH:37]=1)[OH:8])[OH:4]

Participants

5

Reactant 3

HCID 6344DichloromethaneHCID 21893785Acetic Acid Mixture with Hydrobromic AcidHCID 86636536HCID 86636536, compound

Product 1

HCID 66738924HCID 66738924, compoundYield 80%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
10 °C

Procedure

While the internal temperature of the reactor containing 2.622 kg (5.20 mol) of 1-propoxy-2,3,4-tribenzoyl-L-arabinopyranose was maintained at 0-20° C., 4.21 kg of a 30-33% hydrogen bromide/acetic acid solution was added dropwise thereto, and the mixture was stirred at room temperature for 6 hours. After completion of the reaction, 1.296 liters of dichloromethane was added to the reaction solution, which was then stirred for 30 minutes. The stirred solution was added dropwise to a reactor containing 4.162 liters of purified water and stirred for 30 minutes. Then, the stirred solution was separated into layers. The water layer was back-extracted with 1.296 liters of dichloromethane. The oil layer was washed two times with 0.195 kg of aqueous saturated sodium chloride solution and one time with 0.248 kg of aqueous saturated sodium bicarbonate solution, and then dried with sodium sulfate, and the solvent was removed by concentration. To the concentrated residue, 1.30 liters of dichloromethane was added, and the solution was stirred for 2-3 hours. 6.50 liters of hexane was added to the stirred solution, which was then cooled to a temperature of 0-5° C., stirred for 3-4 hours, and filtered. The filtered solids were washed with 2.76 liters of hexane and dried in a vacuum, thus obtaining 2.185 kg (80% yield) of 1-bromo-2,3,4-tribenzoyl-L-arabinopyranose. 1H NMR (CDCl3): δ 8.20-7.90 (dd, 4H), 7.90-7.80 (d, 2H), 7.70-7.20 (m, 9H), 6.93 (d, 1H), 5.97 (dd, 1H), 5.82 (m, 1H), 5.70 (dd, 1H), 4.50 (d, 1H), 4.25 (d, 1H).

Workup

  1. additionwas added to the reaction solution, which
  2. stirringwas then stirred for 30 minutes
  3. additionThe stirred solution was added dropwise to a reactor
  4. stirringstirred for 30 minutes
  5. customThen, the stirred solution was separated into layers
  6. extractionThe water layer was back-extracted with 1.296 liters of dichloromethane
  7. washThe oil layer was washed two times with 0.195 kg of aqueous saturated sodium chloride solution and one time with 0.248 kg of aqueous saturated sodium bicarbonate solution
  8. dry with materialdried with sodium sulfate
  9. customthe solvent was removed by concentration
  10. additionTo the concentrated residue, 1.30 liters of dichloromethane was added
  11. stirringthe solution was stirred for 2-3 hours
  12. addition6.50 liters of hexane was added to the stirred solution, which
  13. temperaturewas then cooled to a temperature of 0-5° C.
  14. stirringstirred for 3-4 hours
  15. filtrationfiltered
  16. washThe filtered solids were washed with 2.76 liters of hexane
  17. customdried in a vacuum

Sources & evidence

ORD record
ord-ca881d6b89fd49d0a153ac4646754b46
Source dataset
uspto-grants-2012_02
Patent number
US08114987B2

Reaction notes

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