Acetovanillone → 4-(3-Chloropropoxy)-3-methoxyacetophenone

HRID 1193634Notes

Reaction equation

HRID 1193634 reaction equation
Br[CH2:2][CH2:3][CH2:4][Cl:5].[CH3:6][C:7]([C:9]1[CH:17]=[CH:16][C:14]([OH:15])=[C:11]([O:12][CH3:13])[CH:10]=1)=[O:8].[OH-].[Na+]>O>[Cl:5][CH2:4][CH2:3][CH2:2][O:15][C:14]1[CH:16]=[CH:17][C:9]([C:7](=[O:8])[CH3:6])=[CH:10][C:11]=1[O:12][CH3:13]

Participants

5

Reactant 3

HCID 2214AcetovanilloneHCID 80061-Bromo-3-chloropropaneHCID 14798Sodium Hydroxide

Product 1

HCID 73142644-(3-Chloropropoxy)-3-methoxyacetophenone

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Conditions

Temperature
86 °C

Procedure

To a mixture of 15.15 kg (96.26 mole) of 1-bromo-3-chloropropane and 25 liter of water heated to 86° C. was added a solution of 8 kg (48.13 mole) of acetovanillone in 3.93 kg (48.6 mole) of 50% aqueous sodium hydroxide and 89 liter of water over a 2.5 hr period. The mixture was heated at 80°-85° C. for 2-5 hr after addition was complete. The mixture was cooled and extracted twice with 49 kg portions of toluene. The combined extracts were washed once with 1.9 kg of 50% sodium hydroxide diluted to 5 gal and once with 5 gal of water. The toluene layer was dried over 3 lb of anhydrous sodium sulfate and concentrated under reduced pressure. The residue was heated to reflux in 15 gal of diisopropylether, filtered, and the filtrate cooled. The crystallized title compound obtained by filtration together with additional compound obtained by concentrating the filtrate to 25% of its original volume amounted to 4.2 kg (36%). Acetovanillone recovered was 3.4 kg. The product was recrystallized twice from cyclohexane and twice from ligroin, m.p. 57.8°-58.5° C.

Workup

  1. temperatureThe mixture was heated at 80°-85° C. for 2-5 hr
  2. additionafter addition
  3. temperatureThe mixture was cooled
  4. extractionextracted twice with 49 kg portions of toluene
  5. washThe combined extracts were washed once with 1.9 kg of 50% sodium hydroxide
  6. additiondiluted to 5 gal and once with 5 gal of water
  7. dry with materialThe toluene layer was dried over 3 lb of anhydrous sodium sulfate
  8. concentrationconcentrated under reduced pressure
  9. temperatureThe residue was heated
  10. temperatureto reflux in 15 gal of diisopropylether
  11. filtrationfiltered
  12. temperaturethe filtrate cooled
  13. customThe crystallized title compound
  14. customobtained by filtration together with additional compound
  15. customobtained
  16. concentrationby concentrating the filtrate to 25% of its original volume
  17. customAcetovanillone recovered
  18. customThe product was recrystallized twice from cyclohexane and twice from ligroin, m.p. 57.8°-58.5° C.

Sources & evidence

ORD record
ord-0bc42a78044041d0987e6fc6a5f62609
Source dataset
uspto-grants-1989_03
Patent number
US04810713

Reaction notes

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