Sulfuric Acid → 2-Bromo-7-iodo-9H-fluorene

HRID 1269130Notes

Reaction equation

HRID 1269130 reaction equation
[Br:1][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[CH:3]=1.S(=O)(=O)(O)O.O.O.[I:22](O)(=O)(=O)=O.S([O-])(O)=O.[Na+]>O.C(O)(=O)C>[Br:1][C:2]1[CH:14]=[CH:13][C:12]2[C:11]3[C:6](=[CH:7][C:8]([I:22])=[CH:9][CH:10]=3)[CH2:5][C:4]=2[CH:3]=1

Participants

7

Reactant 4

HCID 1118Sulfuric AcidHCID 143362-Bromo-9H-fluorene2×HCID 23665763Sodium BisulfiteHCID 86590690HCID 86590690, compound

Product 1

HCID 142909822-Bromo-7-iodo-9H-fluoreneYield 382.7%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 962WaterSolvent3×

Conditions

Temperature
75 °C

Procedure

A mixture of 2-bromofluorene (compound 19) (25.0 g, 0.1020 mol), glacial acetic acid (250 cm3), concentrated sulphuric acid (3 cm3) and water (20 cm3) became homogeneous on heating to 75° C. Periodic acid dihydrate (H5IO6, 4.56 g, 0.0200 mol) and pulverised 12 (10.2 g, 0.0402 mol) were added. The initial deep-purple colour changed to a brown during 2 h of heating and stirring at 75° C. Upon dilution with sodium hydrogensulphite (2.50 g) in water (25 cm3), the colour changed to yellow. The solution was subsequently diluted with water (500 cm3) and cooled to 0° C. to give a yellow precipitate. The excess liquid was decanted and the solid filtered off, washed repeatedly with cold ethanol (4×50 cm3), aqueous NaOH (5% solution, 4×50 cm3) and with water (4×50 cm3) to leave a yellow powder. The product was recrystallised from a solvent mixture of DCM and ethanol to yield a yellow powder (28.4 g, 74.9%). Melting point/° C.: 185.

Workup

  1. additionwere added
  2. custombrown during 2 h
  3. temperatureof heating
  4. temperaturecooled to 0° C.
  5. customto give a yellow precipitate
  6. customThe excess liquid was decanted
  7. filtrationthe solid filtered off
  8. washwashed repeatedly with cold ethanol (4×50 cm3), aqueous NaOH (5% solution, 4×50 cm3) and with water (4×50 cm3)
  9. customto leave a yellow powder
  10. customThe product was recrystallised from a solvent mixture of DCM and ethanol

Sources & evidence

ORD record
ord-7e96d4e891c2428a98c4cd17d3dc13c6
Source dataset
uspto-grants-2007_04
Patent number
US07199167B2

Reaction notes

Loading…