Potassium Iodide → HCID 46193335, compound

HRID 2190898Notes

Reaction equation

HRID 2190898 reaction equation
C(=O)([O-])[O-].[K+].[K+].[I-].[K+].[OH:9][C:10]1[C:23]2[C:22](=[O:24])[C:21]3[C:16](=[CH:17][CH:18]=[CH:19][C:20]=3[OH:25])[C:15](=[O:26])[C:14]=2[CH:13]=[C:12]([CH2:27][OH:28])[CH:11]=1.[CH2:29](Cl)[C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.CN(C=O)C.CO>[CH2:29]([O:9][C:10]1[C:23]2[C:22](=[O:24])[C:21]3[C:16](=[CH:17][CH:18]=[CH:19][C:20]=3[O:25][CH2:27][C:12]3[CH:13]=[CH:14][CH:23]=[CH:10][CH:11]=3)[C:15](=[O:26])[C:14]=2[CH:13]=[C:12]([CH2:27][OH:28])[CH:11]=1)[C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1

Participants

8

Reactant 4

HCID 4875Potassium IodideHCID 7503Benzyl ChlorideHCID 10207Aloe-emodinHCID 11430Potassium Carbonate

Product 1

HCID 46193335HCID 46193335, compoundYield 148.3%

Reagents, catalysts & solvents 3

HCID 74236Tetrabutylammonium BromideCatalystHCID 887MethanolSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
80 °C

Procedure

483 g (3.5 moles) of potassium carbonate, 16 g (0.1 moles) of potassium iodide and 16 g (0.05 moles) of tetrabutylammonium bromide are added to a solution of 270 g (1 mole) of 1,8-dihydroxy-3-(hydroxymethyl)anthraquinone (aloe-emodin) in 3500 ml of DMF at 60° C.; the reaction mixture is heated at 80° C. for 1 h. It is cooled to 50° C. and 443 g (3.5 moles) of benzyl chloride are added dropwise in approximately one hour. At the end of the dripping, the reaction mixture is brought back to 80° C. and left at that temperature under stirring for 45-60 minutes. It is then cooled to 50° C. and 200 ml of methyl alcohol are added. It is cooled to 20-25° C. and the inorganic salts are removed by filtering. The organic solvent is distilled at 60-70° C. at reduced pressure and the residue is dissolved in 3200 ml of tetrahydrofuran at 60° C. Maintaining the temperature at 50-60° C., the organic phase is washed twice with 1200 ml of 2.5 molar aqueous sodium hydroxide and once with 1000 ml of a saturated solution of sodium chloride in water. The organic phase is concentrated at reduced pressure at 60° C. and the residue is recovered with 2700 ml of ethyl acetate. The suspension thus obtained is concentrated to approximately ⅓ of the initial volume by distillation of the solvent at reduced pressure. It is gradually cooled to 0-4° C. and kept at that temperature for 1 hour. The solid is filtered and washed with ethyl acetate (100 ml×2). The damp product is dried at 45° C. at reduced pressure for 12-14 hours, providing 334 g (yield 74%) of dibenzyl aloe-emodin having a purity of 98% (HPLC).

Workup

  1. temperatureIt is cooled to 50° C.
  2. customis brought back to 80° C.
  3. waitleft at that temperature
  4. temperatureIt is then cooled to 50° C.
  5. temperatureIt is cooled to 20-25° C.
  6. customthe inorganic salts are removed
  7. filtrationby filtering
  8. distillationThe organic solvent is distilled at 60-70° C. at reduced pressure
  9. dissolutionthe residue is dissolved in 3200 ml of tetrahydrofuran at 60° C
  10. temperatureMaintaining the temperature at 50-60° C.
  11. washthe organic phase is washed twice with 1200 ml of 2.5 molar aqueous sodium hydroxide and once with 1000 ml of a saturated solution of sodium chloride in water
  12. concentrationThe organic phase is concentrated at reduced pressure at 60° C.
  13. customthe residue is recovered with 2700 ml of ethyl acetate
  14. customThe suspension thus obtained
  15. concentrationis concentrated to approximately ⅓ of the initial volume
  16. distillationby distillation of the solvent at reduced pressure
  17. temperatureIt is gradually cooled to 0-4° C.
  18. waitkept at that temperature for 1 hour
  19. filtrationThe solid is filtered
  20. washwashed with ethyl acetate (100 ml×2)
  21. customThe damp product is dried at 45° C. at reduced pressure for 12-14 hours

Sources & evidence

ORD record
ord-a6e5ad18c5124d9eb2c1cbfee3b2c2be
Source dataset
uspto-grants-2012_12
Patent number
US08324411B2

Reaction notes

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