Hydrochloric Acid → 4,4'-(9H-Fluorene-9,9-diyl)bis(2-methylphenol)

HRID 78960

Reaction equation

HRID 78960 reaction equation
[C:1]1(=O)[C:13]2[C:5]([C:6]3[C:11]([CH:12]=2)=[CH:10][CH:9]=[CH:8][CH:7]=3)=[CH:4][CH:3]=[CH:2]1.[CH3:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=1[OH:22].Cl.[OH-:24].[Na+]>C(S)CCCCCCCCCCC>[OH:22][C:17]1[CH:18]=[CH:19][C:20]([C:13]2([C:1]3[CH:2]=[CH:3][C:6]([OH:24])=[C:5]([CH3:13])[CH:4]=3)[C:5]3[CH:4]=[CH:9][CH:8]=[CH:7][C:6]=3[C:11]3[C:12]2=[CH:1][CH:2]=[CH:3][CH:10]=3)=[CH:21][C:16]=1[CH3:15]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 335O-CresolHCID 14798Sodium HydroxideHCID 22281833Fluoreneone2×

Product 1

HCID 110143454,4'-(9H-Fluorene-9,9-diyl)bis(2-methylphenol)Yield 156.9%

Reagents, catalysts & solvents 1

HCID 81951-DodecanethiolCatalyst

Conditions

Temperature
50 °C

Procedure

A reaction was carried out by (a) feeding 23 g of fluorenone, 1.3 g of dodecyl mercaptan, and 161.0 g of 2-methyl phenol into a 500 ml glass reactor vessel equipped with a stirrer, a condenser and a thermometer, (b) dropping 13.0 g of 35% hydrochloric acid to a mixture, and (c) stirring the mixture at 50° C. for 2 hours. The amount of remaining fluorenone was determined by HPLC, and found to be 0.1% or less. To an obtained reaction mixture liquid, 18.5 g of 29% sodium hydroxide aqueous solution was added, and thereafter 94.0 g of 2-methyl phenol was distilled away from an organic phase by concentration under reduced pressure. To an obtained concentrated liquid, 161 g of toluene and 23 g of water were added, and the mixture liquid was stirred at 80° C. Thereafter, an aqueous phase was separated and removed, and a target substance partitioned in the organic phase was recovered. The organic phase was further washed twice with 23 g of water, and cooled to 10° C. Then, precipitated crystals were subjected to filtration and drying to obtain 37.9 g of 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (yield: 84.3%, LC purity: 99.3%). Obtained 9,9-bis(4-hydroxy-3-methylphenyl)fluorene was dissolved by heat at 230° C. for 2 hours. The 9,9-bis(4-hydroxy-3-methylphenyl)fluorene thus dissolved had a hue of 1 in Gardner. The total amount of toluene used in the production was 4.2 parts by weight relative to 1 part by weight of the 9,9-bis(4-hydroxy-3-methylphenyl)fluorene.

Workup

  1. customequipped with a stirrer, a condenser
  2. additionwas added
  3. distillation94.0 g of 2-methyl phenol was distilled away from an organic phase by concentration under reduced pressure
  4. concentrationTo an obtained concentrated liquid, 161 g of toluene and 23 g of water
  5. additionwere added
  6. stirringthe mixture liquid was stirred at 80° C
  7. customThereafter, an aqueous phase was separated
  8. customremoved
  9. customa target substance partitioned in the organic phase
  10. customwas recovered
  11. washThe organic phase was further washed twice with 23 g of water
  12. temperaturecooled to 10° C
  13. customThen, precipitated crystals
  14. filtrationwere subjected to filtration
  15. customdrying

Sources & evidence

ORD record
ord-eb66a1f238504bd7aa0d3e7dd26b20af
Source dataset
uspto-grants-2014_09
Patent number
US08841491B2

Linked notes

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