4-(4-Aminophenyl)cyclohexan-1-one → 4-(4'-Hydroxyphenyl)cyclohexanone

HRID 484277Notes

Reaction equation

HRID 484277 reaction equation
N[C:2]1[CH:7]=[CH:6][C:5]([CH:8]2[CH2:13][CH2:12][C:11](=[O:14])[CH2:10][CH2:9]2)=[CH:4][CH:3]=1.N([O-])=[O:16].[Na+]>S(=O)(=O)(O)O.O>[OH:16][C:2]1[CH:7]=[CH:6][C:5]([CH:8]2[CH2:13][CH2:12][C:11](=[O:14])[CH2:10][CH2:9]2)=[CH:4][CH:3]=1

Participants

5

Reactant 2

HCID 233718944-(4-Aminophenyl)cyclohexan-1-one2×HCID 23668193Sodium Nitrite2×

Product 1

HCID 45989164-(4'-Hydroxyphenyl)cyclohexanoneYield 84.5%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 1118Sulfuric AcidSolvent2×

Conditions

Temperature
80 °C

Procedure

200 ml of 4 N sulfuric acid were heated to 80° C. in a sulfonation flask and then treated with about 5% of a solution of 37.9 g of 4-(4-aminophenyl)cyclohexanone in 200 ml of 4 N sulfuric acid. Subsequently, the remaining solution of 4-(4-aminophenyl)cyclohexanone as well as a solution of 15.2 g of sodium nitrite in 45 ml of water were simultaneously added dropwise to the reaction mixture at 80° C. within 1.5 hours. Thereafter, the mixture was treated dropwise at 80° C. within 30 minutes with a solution of 9 g of sodium nitrite in 27 ml of water and stirred at 80° C. for a further 1 hour. After cooling the reaction mixture to 0° C. the separated crystals were removed by filtration under suction, washed with 200 ml of cold water and dried up to constant weight at 60° C. in a drying oven under a water-jet vacuum. The crystalline crude product (34.6 g) was suspended in 520 ml of ethyl acetate. The suspension was heated to reflux for 1 hour, then treated with 1.7 g of active carbon and then heated to reflux for a further 1 hour. The mixture was subsequently suction filtered (rinsing with 40 ml of warm ethyl acetate) and the filtrate was evaporated under a water-jet vacuum at a bath temperature of 40° C. Drying of the evaporation residue up to constant weight at 60° C. in a drying oven under a water-jet vacuum gave 32.2 g of 4-(4-hydroxyphenyl)cyclohexanone as yellow-brown crystals with m.p. 165°-166° C.

Workup

  1. temperatureAfter cooling the reaction mixture to 0° C. the separated crystals
  2. customwere removed by filtration under suction
  3. washwashed with 200 ml of cold water
  4. customdried up to constant weight at 60° C. in a drying oven under a water-jet vacuum
  5. temperatureThe suspension was heated
  6. temperatureto reflux for 1 hour
  7. additiontreated with 1.7 g of active carbon
  8. temperatureheated
  9. temperatureto reflux for a further 1 hour
  10. filtrationfiltered
  11. wash(rinsing with 40 ml of warm ethyl acetate)
  12. customthe filtrate was evaporated under a water-jet vacuum at a bath temperature of 40° C
  13. customDrying of the evaporation residue up to constant weight at 60° C. in a drying oven under a water-jet vacuum

Sources & evidence

ORD record
ord-347a2f81db4a49059e7e8d4e9fe331dc
Source dataset
uspto-grants-1993_07
Patent number
US05230826

Reaction notes

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