M-Cresol → HCID 23369052, compound

HRID 1901987Notes

Reaction equation

HRID 1901987 reaction equation
Cl[C:2]1[CH:14]=[CH:13][C:12]2[C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[CH2:5][C:4]=2[C:3]=1Cl.[CH:16]1[C:21]([OH:22])=[CH:20][CH:19]=[CH:18][C:17]=1[CH3:23]>ClCCl>[CH3:5][C:4]1[CH:3]=[CH:2][C:14]2[C:5]3([C:6]4[CH:7]=[CH:8][CH:9]=[CH:10][C:11]=4[C:12]4[C:4]3=[CH:3][CH:2]=[CH:14][CH:13]=4)[C:20]3[C:21]([O:22][C:13]=2[CH:12]=1)=[CH:16][C:17]([CH3:23])=[CH:18][CH:19]=3

Participants

4

Reactant 2

HCID 342M-CresolHCID 218856231,2-Dichloro-9H-fluorene

Product 1

HCID 23369052HCID 23369052, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
40 °C

Procedure

Dichlorofluorene (DCF) (35.27 g, 0.15 mole) is weighed into a powder addition funnel and dissolved in 20 mL of dry dichloromethane. Liquid m-cresol (64.88 g, 0.6 mole) is weighed into a 250 mL three-necked round-bottomed flask which is equipped with a stirrer, heating mantle, nitrogen inlet, condenser, thermometer, and drying tube. Dry dichloromethane (80 mL) is added and the mixture is heated to 40° C. with stirring. DCF solution is added slowly to the mixture as the temperature is maintained at about 40° C. The reaction is rapid as evidenced by copious production of HCl bubbles after each addition. After addition is complete, the reaction is stirred for an additional half hour and then checked by LC. The reaction is complete, and the chromatograph shows peaks for the desired bisphenol (9,9-bis(2-hydroxy-4-methylphenyl)fluorene) along with isomers. The mixture is dissolved in toluene and refluxed with 0.5 mL of methane sulfonic acid collecting water formed during the cyclization reaction in a Dean-Stark trap. The toluene is then removed by rotary evaporation and the residue is slurried with acetonitrile, chilled and filtered to yield the spiroether [3',6'-dimethylspiro[fluorene-9,9'-xanthene] as an off-white powder. The isomeric bisphenols formed in the alkylation reaction do not cyclize and remain dissolved in the acetonitrile.

Workup

  1. customwhich is equipped with a stirrer
  2. temperatureheating mantle, nitrogen inlet, condenser
  3. customthermometer, and drying tube
  4. additionDry dichloromethane (80 mL) is added
  5. additionDCF solution is added slowly to the mixture as the temperature
  6. temperatureis maintained at about 40° C
  7. additionafter each addition
  8. additionAfter addition
  9. stirringthe reaction is stirred for an additional half hour
  10. dissolutionThe mixture is dissolved in toluene
  11. temperaturerefluxed with 0.5 mL of methane sulfonic acid
  12. customcollecting water
  13. customformed during the cyclization reaction in a Dean-Stark trap
  14. customThe toluene is then removed by rotary evaporation
  15. temperaturechilled
  16. filtrationfiltered

Sources & evidence

ORD record
ord-d756d66cd1e74008a115f470bc37bad1
Source dataset
uspto-grants-1996_11
Patent number
US05578737

Reaction notes

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