Sodium Iodide → HCID 69082490, compound

HRID 2205579Notes

Reaction equation

HRID 2205579 reaction equation
OC1C=CC(C(C2C=CC=CC=2)=O)=CC=1.BrCCCCl.C(=O)([O-])[O-].[K+].[K+].Cl[CH2:28][CH2:29][CH2:30][O:31][C:32]1[CH:45]=[CH:44][C:35]([C:36]([C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)=[O:37])=[CH:34][CH:33]=1.C(C1C=CC(OCCCOC2C=CC(C(=O)C3C=CC=CC=3)=CC=2)=CC=1)(=O)C1C=CC=CC=1.[NH:79]([CH2:83][CH2:84][OH:85])[CH2:80][CH2:81][OH:82].[I-].[Na+]>CC(C)CC(=O)C>[OH:82][CH2:81][CH2:80][N:79]([CH2:83][CH2:84][OH:85])[CH2:28][CH2:29][CH2:30][O:31][C:32]1[CH:45]=[CH:44][C:35]([C:36]([C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)=[O:37])=[CH:34][CH:33]=1

Participants

9

Reactant 7

HCID 5238Sodium IodideHCID 80061-Bromo-3-chloropropaneHCID 8113DiethanolamineHCID 11430Potassium CarbonateHCID 143474-Hydroxybenzophenone2×HCID 10934655HCID 10934655, compoundHCID 20340702HCID 20340702, compound

Product 1

HCID 69082490HCID 69082490, compoundYield 89%

Reagents, catalysts & solvents 1

HCID 7909Methyl Isobutyl KetoneSolvent2×

Conditions

Temperature
120 °C

Procedure

A 500 mL three-neck flask was charged with 4-hydroxybenzophenone (80.00 g; 0.4036 mol), 1-bromo-3-chloropropane (76.25 g; 0.4843 mol) and 4-methyl-2-pentanone (330 mL). Anhydrous potassium carbonate (61.36 g; 0.4440 mol) was added and the reaction mixture was stirred at reflux (120° C.) for 4 h. HPLC analysis shows that the reaction mixture contains 90.0% 4-(3-chloropropoxy)benzophenone; 7.0% 1,3-bis(4-benzoylphenoxy)propane and 0.8% 4-hydroxybenzophenone. The reaction mixture was filtered hot and the inorganic solids were washed with 4-methyl-2-pentanone (100 mL). The filtrate was charged into a mixture of diethanolamine (148.5 g; 1.412 mol), sodium iodide (6.05 g; 0.0404 mol) and 4-methyl-2-pentanone (150 mL). The reaction mixture heated to reflux (122° C.) for 24 h. The reaction mixture was cooled to room temperature and extracted with water (500 mL). The organic phase was extracted with 1 M HCl (500 mL) at 70° C. to prevent crystallisation of the 1,3-bis(4-benzoylphenoxy)propane byproduct. The aqueous phase was separated, cooled to room temperature and taken to pH 12 with 50% aqueous NaOH. The resulting emulsion was extracted with 4-methyl-2-pentanone (3×200 mL). The organic phase was separated, dried (MgSO4), filtered and the solvent removed in vacuo. This provides 4-{3-[bis(2-hydroxyethyl)amino]propoxy}benzophenone (123.2 g; 89% yield over 3 steps).

Workup

  1. filtrationThe reaction mixture was filtered hot
  2. washthe inorganic solids were washed with 4-methyl-2-pentanone (100 mL)
  3. temperatureThe reaction mixture heated
  4. temperatureto reflux (122° C.) for 24 h
  5. temperatureThe reaction mixture was cooled to room temperature
  6. extractionextracted with water (500 mL)
  7. extractionThe organic phase was extracted with 1 M HCl (500 mL) at 70° C.
  8. customcrystallisation of the 1,3-bis(4-benzoylphenoxy)propane byproduct
  9. customThe aqueous phase was separated
  10. temperaturecooled to room temperature
  11. extractionThe resulting emulsion was extracted with 4-methyl-2-pentanone (3×200 mL)
  12. customThe organic phase was separated
  13. dry with materialdried (MgSO4)
  14. filtrationfiltered
  15. customthe solvent removed in vacuo

Sources & evidence

ORD record
ord-b9a9b7754c6c4cf0a3b86dedb3867e79
Source dataset
uspto-grants-2016_06
Patent number
US09371308B2

Reaction notes

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