Toluene → Phenyl 1-hydroxy-2-naphthoate

HRID 1262972Notes

Reaction equation

HRID 1262972 reaction equation
[C:1]1([OH:11])[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH:4]=[CH:3][CH:2]=1.C1(C)C=CC=CC=1.[Cl-].[Al+3].[Cl-].[Cl-].Cl[C:24]([O:26][C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)=[O:25]>O>[OH:11][C:1]1[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH:4]=[CH:3][C:2]=1[C:24]([O:26][C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)=[O:25]

Participants

6

Reactant 4

HCID 1140TolueneHCID 70051-NaphtholHCID 15891Phenyl chloroformateHCID 6451240Aluminum(III) Chloride

Product 1

HCID 67236Phenyl 1-hydroxy-2-naphthoateYield 59.7%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Procedure

To a 500-mL, three-neck, nitrogen-purged flask were added 28.8 g (0.20 mole) of 1-naphthol and 90 mL of toluene. To this stirred slurry was added 26.6 g (0.20 mole) of anhydrous aluminum chloride in portions over five minutes. The temperature of the mixture rose to 40°-50° C. during this addition. The orange slurry was heated to reflux, then 32.0 g (0.204 mole) of phenyl chloroformate was added over a period of 30 minutes. After this addition, the mixture was refluxed for 30 minutes then cooled to 30°-40° C. To the red reaction mixture was added 100 mL of water while holding the temperature at 35°-50° C. This addition is very exothermic initially, and ice bath cooling is used. During addition of the remaining water, the bath is lowered or removed in order to avoid cooling below 35° C. After this addition, 20 mL of 32% hydrochloric acid was added quickly at 35° -50° C. The mixture was stirred for 15 minutes, then the layers are allowed to separate. The lower (aqueous) layer was discarded. The top layer was washed (at 40°-50° C.) successively with: two 100-mL portions of 10% hydrochloric acid and two 100-mL portions of 40°-50° C. water. The solvent was then stripped off under vacuum (150-200 mm) to a pot temperature of 90° C. To the resulting amber liquid was added 120 mL of isopropyl alcohol at 70° C. The solution was cooled slowly to 0°-5° C. After stirring at 0°-5° C. for one hour, the slurry was filtered and the solids washed with three 25-mL portions of 0°-5° C. isopropyl alcohol. The yellow solids were air dried at 40° C. to give 31.5 g (59.7%) of phenyl 1-hydroxy-2-naphthoate.

Workup

  1. customTo a 500-mL, three-neck, nitrogen-purged flask
  2. additionThe temperature of the mixture rose to 40°-50° C. during this addition
  3. temperatureThe orange slurry was heated
  4. temperatureto reflux
  5. additionAfter this addition
  6. temperaturethe mixture was refluxed for 30 minutes
  7. temperaturethen cooled to 30°-40° C
  8. customTo the red reaction mixture
  9. customat 35°-50° C
  10. additionThis addition
  11. temperatureice bath cooling
  12. customremoved in order
  13. temperatureto avoid cooling below 35° C
  14. additionAfter this addition, 20 mL of 32% hydrochloric acid
  15. additionwas added quickly at 35° -50° C
  16. customto separate
  17. washThe top layer was washed (at 40°-50° C.) successively with: two 100-mL portions of 10% hydrochloric acid and two 100-mL portions of 40°-50° C. water
  18. customwas then stripped off under vacuum (150-200 mm) to a pot temperature of 90° C
  19. additionTo the resulting amber liquid was added 120 mL of isopropyl alcohol at 70° C
  20. temperatureThe solution was cooled slowly to 0°-5° C
  21. stirringAfter stirring at 0°-5° C. for one hour
  22. filtrationthe slurry was filtered
  23. washthe solids washed with three 25-mL portions of 0°-5° C. isopropyl alcohol
  24. customdried at 40° C.

Sources & evidence

ORD record
ord-46c499abf0f64cf794fbd3eace2c476c
Source dataset
uspto-grants-1984_06
Patent number
US04454340

Reaction notes

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