O-Cresol → HCID 19387417, compound

HRID 2399271Notes

Reaction equation

HRID 2399271 reaction equation
O[C:2]1([C:15]2[CH:20]=[CH:19][C:18]([O:21][CH3:22])=[CH:17][CH:16]=2)[C:14]2[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=2[C:8]2[C:3]1=[CH:4][CH:5]=[CH:6][CH:7]=2.[C:23]1([CH3:30])[C:28]([OH:29])=[CH:27][CH:26]=[CH:25][CH:24]=1.OS(O)(=O)=O.[OH-].[Na+]>C(O)(=O)C.O>[CH3:22][O:21][C:18]1[CH:17]=[CH:16][C:15]([C:2]2([C:25]3[CH:26]=[CH:27][C:28]([OH:29])=[C:23]([CH3:30])[CH:24]=3)[C:3]3[CH:4]=[CH:5][CH:6]=[CH:7][C:8]=3[C:9]3[C:14]2=[CH:13][CH:12]=[CH:11][CH:10]=3)=[CH:20][CH:19]=1

Participants

7

Reactant 4

HCID 335O-CresolHCID 1118Sulfuric AcidHCID 14798Sodium HydroxideHCID 2762179-(4-Methoxyphenyl)-9H-fluoren-9-ol

Product 1

HCID 19387417HCID 19387417, compoundYield 95.2%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 962WaterSolvent

Procedure

4-Bromoanisole (46.7 g) was added dropwise to a stirred mixture of magnesium (6.0 g) in dry THF (250 mL). When all the magnesium had dissolved, 9-fluorene (40.0 g) in THF (400 mL) was added dropwise. The mixture was then stirred at room temperature for 3 hours and quenched with saturated ammonium chloride solution. The excess solvent was evaporated in vacuo and the residue extracted with ethyl acetate. The organic layers were dried (MgSO4), filtered, evaporated and recrystallized from hexane/ether to give 9-hydroxy-9-(4-methoxyphenyl)fluorene as a solid (48.2 g) M.P. 91°-93° C. This trityl alcohol (3.2 g) and o-cresol (1.8 g) were dissolved in acetic acid (25 mL) and concentrated H2SO4) (0.5 mL) was added dropwise. A deep red color developed rapidly and the reaction mixture decolorized after 30 seconds. After five minutes, the mixture was poured into water, neutralized with NaOH solution, and extracted with ethyl acetate. The organic layers were dried (MgSO4), filtered, evaporated in vacuo to give 9-(4-methoxyphenyl)-9-(3-methyl-4-hydroxyphenyl)fluorene (4.0 g) as an oil, which was used in the next step without further purification. Ethanethiol (3.7 g) was added dropwise to a stirred suspension of sodium hydride (2.3 g, 60% in mineral oil) in dry DMF (20mL). After the hydrogen bubbling had ceased, the above-mentioned oil was added and the mixture refluxed for 2 hours under nitrogen. The excess solvent was evaporated in vacuo and the residue extracted with ethyl acetate. The organic layers were dried (MgSO4), filtered, evaporated in vacuo and the residue recrystallized from chloroform-hexane to give the title compound (2.5 g) as a solid. M.P. 186°-188° C.

Workup

  1. waitAfter five minutes
  2. extractionextracted with ethyl acetate
  3. dry with materialThe organic layers were dried (MgSO4)
  4. filtrationfiltered
  5. customevaporated in vacuo

Sources & evidence

ORD record
ord-39b1e97cbab74e6882f3b19400502c9f
Source dataset
uspto-grants-1995_09
Patent number
US05447960

Reaction notes

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