Benzyl Chloride → HCID 131711789, compound

HRID 1706584Notes

Reaction equation

HRID 1706584 reaction equation
[CH2:1]1[O:11][C@@H:10]([CH2:12][OH:13])[C@H:8]([OH:9])[C@@H:6]([OH:7])[C@@:2]1([OH:5])[CH2:3][OH:4].[CH2:14](Cl)[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1.[OH-].[K+]>O>[CH2:14]([O:4][CH2:3][C@:2]1([CH2:1][O:11][C@@H:10]([CH2:12][O:13][CH2:14][C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)[C@H:8]([O:9][CH2:14][C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)[C@H:6]1[O:7][CH2:14][C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)[OH:5])[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1

Participants

5

Reactant 3

HCID 7503Benzyl ChlorideHCID 14797Potassium HydroxideHCID 131711790HCID 131711790, compound

Product 1

HCID 131711789HCID 131711789, compoundYield 71%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

A vigorously stirred mixture of 2,5-O-methylene-L-mannitol (8.0 g.), benzyl chloride (80.0 ml.), and powdered potassium hydroxide (40.0 g.) was slowly heated to 115°-125° and kept in this temperature range for six hours. The mixture was then cooled, water (200 ml.) added, and the mixture was steam distilled for 5 hours. The solution was then cooled, the organic layer (lower) separated in a separatory funnel and the aqueous layer extracted with three 100 ml. portions of ether which were then added to the organic layer. The combined organic layer was then extracted with three 100 ml. portions of water, dried over magnesium sulfate, and evaporated under reduced pressure to a syrup. The syrup was dissolved in methanol (35 ml.) and the solution cooled in an ice bath. Water was added until turbidity persisted and the solution was left to stand at 5° overnight. The crystalline product was removed by filtration, dissolved in isopropyl ether to which was added some methanol, and the resultant solution cooled at 5° while crystallization progressed. The filtered crystals were washed with a solution of pentane-isopropyl ether (1:2, v/v) and air dried to give pure 1,3,4,6-tetra-O-benzyl-2,5-O-methylene-L-mannitol (16.2 g. 71%) having m.p. 53°-54°, and [α]D +6.4° (c 1.09, chloroform) as compared with m.p. 55°-56°, and [α]D -6.6° (c 1.02, chloroform) which were found for the D-isomer.

Workup

  1. temperaturewas slowly heated to 115°-125°
  2. temperatureThe mixture was then cooled
  3. distillationdistilled for 5 hours
  4. temperatureThe solution was then cooled
  5. customthe organic layer (lower) separated in a separatory funnel
  6. extractionthe aqueous layer extracted with three 100 ml
  7. additionportions of ether which were then added to the organic layer
  8. extractionThe combined organic layer was then extracted with three 100 ml
  9. dry with materialportions of water, dried over magnesium sulfate
  10. customevaporated under reduced pressure to a syrup
  11. dissolutionThe syrup was dissolved in methanol (35 ml.)
  12. temperaturethe solution cooled in an ice bath
  13. additionWater was added until turbidity
  14. waitthe solution was left
  15. waitto stand at 5° overnight
  16. customThe crystalline product was removed by filtration
  17. dissolutiondissolved in isopropyl ether to which
  18. additionwas added some methanol
  19. temperaturethe resultant solution cooled at 5° while crystallization
  20. washThe filtered crystals were washed with a solution of pentane-isopropyl ether (1:2
  21. customv/v) and air dried

Sources & evidence

ORD record
ord-469bb9469def46788fd794e0fa5d8700
Source dataset
uspto-grants-1980_06
Patent number
US04207413

Reaction notes

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