O-Cresol → 4,4'-(9H-Fluorene-9,9-diyl)bis(2-methylphenol)

HRID 78963Notes

Reaction equation

HRID 78963 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]>O.OP(O)(O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O>[OH:22][C:17]1[CH:18]=[CH:19][C:20]([C:13]2([C:1]3[CH:2]=[CH:3][C:17]([OH:22])=[C:16]([CH3:21])[CH:15]=3)[C:5]3[CH:4]=[CH:9][CH:8]=[CH:7][C:6]=3[C:11]3[C:12]2=[CH:18][CH:19]=[CH:20][CH:10]=3)=[CH:21][C:16]=1[CH3:15]

Participants

4

Reactant 2

HCID 335O-CresolHCID 22281833Fluoreneone

Product 1

HCID 110143454,4'-(9H-Fluorene-9,9-diyl)bis(2-methylphenol)Yield 83.5%

Reagents, catalysts & solvents 1

HCID 16212977Phosphoric acid--trioxotungsten--water (1/12/1)Catalyst

Conditions

Temperature
80 °C

Procedure

A reaction was carried out by (a) feeding 23 g of fluorenone, 0.57 g of tungstophosphoric acid, and 161 g of 2-methyl phenol into a 500 ml glass reactor vessel equipped with a stirrer, a condenser and a thermometer, and (b) stirring a mixture under a reduced pressure of 1.3×103 Pa at 70° C. for 4 hours while removing generated water out of the system. The amount of remaining fluorenone was determined by HPLC, and found to be 0.1% or less. To an obtained reaction mixture liquid, 0.6 g of 29% sodium hydroxide aqueous solution was added, and 103.5 g of 2-methyl phenol was recovered from an organic phase by concentration under reduced pressure. To a concentrated liquid, 161 g of toluene and 46 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 an organic phase was recovered. The organic phase was further washed twice with 46 g of water, and cooled to 10° C. Then, precipitated crystals were subjected to filtration and drying to obtain 40.3 g of 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (yield: 83.5%, 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 show a hue of 1 or less in Gardner. The total amount of toluene used was 4 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. customwhile removing
  3. customTo an obtained reaction mixture liquid, 0.6 g of 29% sodium hydroxide aqueous solution
  4. additionwas added
  5. custom103.5 g of 2-methyl phenol was recovered from an organic phase by concentration under reduced pressure
  6. additionTo a concentrated liquid, 161 g of toluene and 46 g of water were added
  7. customThereafter, an aqueous phase was separated
  8. customremoved
  9. customa target substance partitioned in an organic phase
  10. customwas recovered
  11. washThe organic phase was further washed twice with 46 g of water
  12. temperaturecooled to 10° C
  13. customThen, precipitated crystals
  14. filtrationwere subjected to filtration
  15. customdrying

Sources & evidence

ORD record
ord-391c4d8375f34d0f9b61a17e031d0e19
Source dataset
uspto-grants-2014_09
Patent number
US08841491B2

Reaction notes

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