Phloroglucinol → HCID 54436545, compound

HRID 1706585Notes

Reaction equation

HRID 1706585 reaction equation
[CH2:1]([O:8][CH2:9][C@:10]1(C[O:31][C@@H:30]([CH2:33][O:34][CH2:35][C:36]2[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=2)[C@H:21]([O:22][CH2:23][C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[C@H:12]1[O:13][CH2:14][C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)[OH:11])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C1(C=C(O)C=C(O)C=1)O>O1CCOCC1.Cl>[CH2:1]([O:8][CH2:9][C@@H:10]([C@@H:12]([C@H:21]([C@H:30]([CH2:33][O:34][CH2:35][C:36]1[CH:37]=[CH:38][CH:39]=[CH:40][CH:41]=1)[OH:31])[O:22][CH2:23][C:24]1[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=1)[O:13][CH2:14][C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)[OH:11])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 2

HCID 359PhloroglucinolHCID 131711789HCID 131711789, compound

Product 1

HCID 54436545HCID 54436545, compound

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolvent2×HCID 312751,4-DioxaneSolvent

Procedure

1,3,4,6-Tetra-O-benzyl-2,5-O-methylene-L-mannitol (7.5 g.) and phloroglucinol (14.3 g.) were dissolved in 1,4-dioxane (400 ml.) and the solution was diluted with 0.6 M hydrochloric acid (290 ml.). The reaction mixture was boiled gently under reflux for 24 hours, at which time t.l.c. (Solvent C) showed the hydrolysis to be complete. To this solution was then added concentrated hydrochloric acid (30 ml.) and heating was continued for a further 12 hours. The mixture was then cooled and concentrated under reduced pressure to a dry crystalline mass which was shaken with dichloromethane (75 ml.) at room temperature. Unchanged phloroglucinol was removed by filtration and washed with more dichloromethane (40 ml.). The combined filtrate and washings were washed with aqueous sodium hydrogen carbonate (saturated solution) and then with water. The solution was dried over magnesium sulfate, filtered through a pad of Celite and decolorizing charcoal and then concentrated to a syrup which was dissolved in a 5:6 mixture of ether and pentane. Crystallization was allowed to progress at 5° to give 5.5 g. (75%) of product in two crops. The product was recrystallized from isopropyl ether to give pure 1,3,4,6-tetra-O-benzyl-L-mannitol, m.p. 52.5°-53°, [α]D -31.5° (c 2.6, chloroform). These values compared favourably with the data obtained for the D-isomer m.p. 55°-56°, and [α]D +31.2° (c 0.87, chloroform).

Workup

  1. temperatureunder reflux for 24 hours, at which time t.l.c
  2. customthe hydrolysis
  3. temperatureheating
  4. temperatureThe mixture was then cooled
  5. concentrationconcentrated under reduced pressure to a dry crystalline mass which
  6. customUnchanged phloroglucinol was removed by filtration
  7. washwashed with more dichloromethane (40 ml.)
  8. washThe combined filtrate and washings were washed with aqueous sodium hydrogen carbonate (saturated solution)
  9. dry with materialThe solution was dried over magnesium sulfate
  10. filtrationfiltered through a pad of Celite
  11. concentrationconcentrated to a syrup which
  12. dissolutionwas dissolved in a 5:6 mixture of ether and pentane
  13. customCrystallization
  14. customto progress at 5°
  15. customto give 5.5 g
  16. customThe product was recrystallized from isopropyl ether

Sources & evidence

ORD record
ord-26351f5a026a43dba2ded82b2f3edb6e
Source dataset
uspto-grants-1980_06
Patent number
US04207413

Reaction notes

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