Iodine → 2-Iodo-9-fluorenone

HRID 1865059Notes

Reaction equation

HRID 1865059 reaction equation
S(=O)(=O)(O)O.[CH:6]1[C:18]2[C:17](=[O:19])[C:16]3[C:11](=[CH:12][CH:13]=[CH:14][CH:15]=3)[C:10]=2[CH:9]=[CH:8][CH:7]=1.II.[I:22](O)(=O)(=O)=O>C(O)(=O)C.O>[I:22][C:14]1[CH:13]=[CH:12][C:11]2[C:10]3[C:18](=[CH:6][CH:7]=[CH:8][CH:9]=3)[C:17](=[O:19])[C:16]=2[CH:15]=1

Participants

7

Reactant 4

HCID 807IodineHCID 1118Sulfuric AcidHCID 10241FluorenoneHCID 65185Metaperiodic acid

Product 1

HCID 2486172-Iodo-9-fluorenoneYield 266.6%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolvent2×HCID 962WaterSolvent

Conditions

Temperature
45 °C

Procedure

Add acetic acid (45 mL), concentrated sulfuric acid (5.4 grams, 0.055 moles), water (10 mL), 9-fluoreneone (9.01 grams, 0.05 moles), iodine (6.0 grams, 0.0237 moles), and periodic acid (2.85 grams, 0.0125 moles) to a 250 mL, 3-neck round-bottom flask equipped with a magnetic stirrer, internal temperature probe, heating mantle, and a glycol-cooled condenser fitted with a nitrogen inlet. Heat the reaction mixture to 45° C. and stir 1 hour, then warm to 50° C. and stir an additional 2.5 hrs. Warm the mixture to 60° C. and add additional acetic acid (45 mL). Stir the reaction mixture for an additional 10 hours, cool to room temperature and stir the reaction mixture at room temperature for about 8 hours. Collect the precipitate by filtration. Transfer the filter cake and acetic acid (40 mL) to a 250 mL, 3-neck round-bottom flask equipped with a magnetic stirrer, internal temperature probe, heating mantle, and a glycol-cooled condenser fitted with a nitrogen inlet. Heat the mixture to 70° C. and add additional acetic acid with continued warming until a clear solution is observed. Reduce the reaction mixture to 50° C. and stir at 50° C. for 2 hours. Slowly cool the reaction mixture to 25° C. and stir 1 hour. Recover the precipitate by vacuum filtration. Air-dried the resulting filter cake to provide the title compound (10.2 g, 66.6% yield). 1H NMR (CDCl3, 500.0 MHz): δ 7.95 (d, 1H, J=1.5); 7.81 (dd, 1H, J=2, 8); 7.64 (d, 1H, J=7.5); 7.50 (m, 2H); 7.33-7.24 (m, 2H).

Workup

  1. customequipped with a magnetic stirrer
  2. temperatureinternal temperature probe, heating mantle
  3. customfitted with a nitrogen inlet
  4. temperaturewarm to 50° C.
  5. stirringstir an additional 2.5 hrs
  6. temperatureWarm the mixture to 60° C.
  7. stirringStir the reaction mixture for an additional 10 hours
  8. temperaturecool to room temperature
  9. stirringstir the reaction mixture at room temperature for about 8 hours
  10. customCollect the precipitate
  11. filtrationby filtration
  12. customequipped with a magnetic stirrer
  13. temperatureinternal temperature probe, heating mantle
  14. temperaturea glycol-cooled condenser
  15. customfitted with a nitrogen inlet
  16. temperatureHeat the mixture to 70° C.
  17. additionadd additional acetic acid
  18. temperaturewith continued warming until a clear solution
  19. customto 50° C.
  20. stirringstir at 50° C. for 2 hours
  21. temperatureSlowly cool the reaction mixture to 25° C.
  22. stirringstir 1 hour
  23. customRecover the precipitate
  24. filtrationby vacuum filtration
  25. customAir-dried the resulting
  26. filtrationfilter cake

Sources & evidence

ORD record
ord-2367aab8272349bebcbf6ba7690ca3df
Source dataset
uspto-grants-2009_12
Patent number
US07625932B2

Reaction notes

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