Реакция #166145

ord-391c4d8375f34d0f9b61a17e031d0e19

Уравнение реакции

O=C1C=CC=C2C1=Cc1ccccc12
fluorenone
Cc1ccccc1O
2-methyl phenol
→
Cc1cc(C2(c3ccc(O)c(C)c3)c3ccccc3-c3ccccc32)ccc1O
9,9-bis(4-hydroxy-3-methylphenyl)fluorene
Выход 83.5%

Реактанты

—
( b )
—
( a )
O=C1C=CC=C2C1=Cc1ccccc12
fluorenone
Cc1ccccc1O
2-methyl phenol

Реагенты

O.O=P(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]
tungstophosphoric acid

Условия реакции

Температура
80°CELSIUS
Подробные условия
See reaction.notes.procedure_details.

Обработка

  1. 1
    Другоеequipped with a stirrer, a condenser
  2. 2
    Другоеwhile removing
  3. 3
    ДругоеTo an obtained reaction mixture liquid, 0.6 g of 29% sodium hydroxide aqueous solution
  4. 4
    workup.ADDITIONwas added
  5. 5
    Другое103.5 g of 2-methyl phenol was recovered from an organic phase by concentration under reduced pressure
  6. 6
    workup.ADDITIONTo a concentrated liquid, 161 g of toluene and 46 g of water were added
  7. 7
    ДругоеThereafter, an aqueous phase was separated
  8. 8
    Другоеremoved
  9. 9
    Другоеa target substance partitioned in an organic phase
  10. 10
    Другоеwas recovered
  11. 11
    ПромывкаThe organic phase was further washed twice with 46 g of water
  12. 12
    Температураcooled to 10° C
  13. 13
    ДругоеThen, precipitated crystals
  14. 14
    Фильтрацияwere subjected to filtration
  15. 15
    Другоеdrying

Методика

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.

Источник

DOI: 10.6084/m9.figshare.5104873.v1Патент: US08841491B2uspto-grants-2014_09