Isophthaloyl chloride → 1,3-Bis(4-fluorobenzoyl)benzene

HRID 333203

Reaction equation

HRID 333203 reaction equation
[Cl-].[Cl-].[Cl-].[Al+3].[C:5](Cl)(=[O:15])[C:6]1[CH:14]=[CH:13][CH:12]=[C:8]([C:9](Cl)=[O:10])[CH:7]=1.[F:17][C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1.[OH-].[Na+]>ClCCl>[F:17][C:18]1[CH:23]=[CH:22][C:21]([C:5]([C:6]2[CH:14]=[CH:13][CH:12]=[C:8]([C:9](=[O:10])[C:21]3[CH:22]=[CH:23][C:18]([F:17])=[CH:19][CH:20]=3)[CH:7]=2)=[O:15])=[CH:20][CH:19]=1

Participants

6

Reactant 4

HCID 7451Isophthaloyl chlorideHCID 10008FluorobenzeneHCID 14798Sodium HydroxideHCID 6451240Aluminum(III) Chloride

Product 1

HCID 6882631,3-Bis(4-fluorobenzoyl)benzeneYield 71.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Aluminum trichloride (6.53 g, 49.5 mmol) was added to a solution of isophthaloyl dichloride (5.0 g, 24.8 mmol) in dichloromethane (100 mL). After heating at reflux for 30 min, the monofluorobenzene (2.835 g, 29.5 mmol) was added and stirring was continued at reflux. After stirring over 12 h, the reaction mixture was poured onto the crushed ice. The resulting solution was neutralized with 10% NaOH (100 mL), and extracted with dichloromethane (3×100 mL). The combined organic layer was washed with water, followed by brine and dried over Na2SO4. After the organic layer was concentrated under reduced pressure, purification using flash chromatography (silica gel, hexanes:ethyl acetate, 60:40) afforded 1,3-bis-(4-fluorobenzoyl)benzene 12 (3.37 g, 10.5 mmol) as a white solid in a 42% yield; 1H NMR (500 MHz, CDCl3): δ 8.130 (t, J=1.5 Hz, 1H, ArH), 8.00 (dd, J=7.5 Hz, 1.5 Hz, 1H, ArH), 7.87 (m, 4H, ArH), 7.64 (t, J=8.0 Hz, 1H, ArH), 7.18 (m, 4H, ArH).

Workup

  1. temperatureAfter heating
  2. temperatureat reflux for 30 min
  3. temperatureat reflux
  4. stirringAfter stirring over 12 h
  5. extractionextracted with dichloromethane (3×100 mL)
  6. washThe combined organic layer was washed with water
  7. dry with materialdried over Na2SO4
  8. concentrationAfter the organic layer was concentrated under reduced pressure, purification

Sources & evidence

ORD record
ord-59a11b20ad254b64b27ab5d58f00effe
Source dataset
uspto-grants-2014_11
Patent number
US08877967B2

Linked notes

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