Hydrochloric Acid → 1,1'-(9H-Fluorene-2,5-diyl)di(ethan-1-one)

HRID 1288106Notes

Reaction equation

HRID 1288106 reaction equation
[C:1](OC(=O)C)(=[O:3])[CH3:2].[Cl-].[Al+3].[Cl-].[Cl-].[C:12]([C:15]1[C:27]2[C:26]3[C:21](=[CH:22][CH:23]=[CH:24][CH:25]=3)[CH2:20][C:19]=2[CH:18]=[CH:17][CH:16]=1)(=[O:14])[CH3:13].Cl>ClC(Cl)C>[C:1]([C:23]1[CH:24]=[CH:25][C:26]2[C:27]3[C:19](=[CH:18][CH:17]=[CH:16][C:15]=3[C:12](=[O:14])[CH3:13])[CH2:20][C:21]=2[CH:22]=1)(=[O:3])[CH3:2]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 7918Acetic AnhydrideHCID 6451240Aluminum(III) ChlorideHCID 20272030HCID 20272030, compound

Product 1

HCID 131337561,1'-(9H-Fluorene-2,5-diyl)di(ethan-1-one)

Reagents, catalysts & solvents 1

HCID 63651,1-DichloroethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

Acetic anhydride (17.7 g.) was added to a stirred suspension of aluminium chloride (64 g.) in dichloroethane (100 ml.). The resulting solution was cooled to 0° C and treated dropwise with stirring, below 10° C, with a solution of 4-acetylfluorene (27.86 g.) in dichloroethane (100 ml.). The mixture was stirred at room temperature for 1 hour and then at 40° C for 3 hours, and finally cooled to 0° C and decomposed with 2N hydrochloric acid (200 ml.). The dichloroethane solution was separated and the aqueous portion was extracted with chloroform. The combined organic solution was washed with water and with aqueous sodium bicarbonate, dried over sodium sulphate and evaporated under reduced pressure. The residual solid was twice recrystallised from ethanol to give pure 2,5-diacetylfluorene, m.pt. 128°-129°. A solution of sodium hydroxide (27.2 g.) in water (500 ml.) was cooled to 0° C, stirred, and treated dropwise with bromine (14.8 ml.). 2,5-Diacetylfluorene (5g.) was added, the temperature was raised to 60° C over 3 hours and kept at 60° C for 3 hours. The mixture was cooled and filtered and the filtrate was warmed to 60° C, treated with sodium acetate (230 g.) and then cooled to 0° C for 1 hour. The resulting yellow precipitate was dissolved in water (200 ml.) and the solution was acidified with concentrated hydrochloric acid. After heating on the steam bath for 1 hour the solid was filtered, washed with water and dried in vacuo to give fluorenone-2,5-dicarboxylic acid m.pt. 300° C.

Workup

  1. additiontreated dropwise
  2. waitat 40° C for 3 hours
  3. temperaturefinally cooled to 0° C
  4. customThe dichloroethane solution was separated
  5. extractionthe aqueous portion was extracted with chloroform
  6. washThe combined organic solution was washed with water and with aqueous sodium bicarbonate
  7. dry with materialdried over sodium sulphate
  8. customevaporated under reduced pressure
  9. customThe residual solid was twice recrystallised from ethanol

Sources & evidence

ORD record
ord-04299eea400344daa50b96fd87417dcc
Source dataset
uspto-grants-1976_10
Patent number
US03987088

Reaction notes

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