Hydrochloric Acid → 1,4-Bis(4-fluorophenyl)but-2-ene-1,4-dione

HRID 1464624Notes

Reaction equation

HRID 1464624 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Cl-].[Al+3].[Cl-].[Cl-].[C:12](Cl)(=[O:18])/[CH:13]=[CH:14]/[C:15](Cl)=[O:16].Cl>C(=S)=S>[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:12]([CH:13]=[CH:14][C:15](=[O:16])[C:5]2[CH:6]=[CH:7][C:2]([F:1])=[CH:3][CH:4]=2)=[O:18])=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 10008FluorobenzeneHCID 5325504Fumaryl chlorideHCID 6451240Aluminum(III) Chloride

Product 1

HCID 5202211,4-Bis(4-fluorophenyl)but-2-ene-1,4-dioneYield 96%

Reagents, catalysts & solvents 1

HCID 6348Carbon DisulfideSolvent

Procedure

To a solution of fluorobenzene (0.52 mols, 50 g, 48.83 mL) in carbon disulfide (500 mL) was added aluminium chloride (0.651 mmol, 86.8 g). The resulting suspension was gently refluxed under an atmosphere of nitrogen. Fumaryl chloride (0.26 mols, 28.2 mL) was added over a period of 15-20 minutes. The resulting dark orange reaction mixture was refluxed for 18 h and the residue was poured into crushed ice (1 Kg) and concentrated hydrochloric acid (15.0 mL). The semi-solid was filtered off, washed with ether and ethanol, digested in ethanol, and recrystallized from ethyl acetate/ethanol to give pale yellow needles of compound 1 in 96% yield, m.p. 115°-116° C. 1H NMR: 7.14-7.18 (t, 2H, Jmeta =1.9 Hz, C6H4), 7.96 (s, 2H, CH=CH), 8.05-8.12 (q, 6H, J=2.2 Hz, C6H4); ms m/e (Cl with NH3 ), 290(NH3 +H+M), 273(M+1), 272(M); HRMS m/e calcd for C16H10O2F2 273.0727, found 273.0727.

Workup

  1. temperatureThe resulting suspension was gently refluxed under an atmosphere of nitrogen
  2. temperatureThe resulting dark orange reaction mixture was refluxed for 18 h
  3. additionthe residue was poured
  4. filtrationThe semi-solid was filtered off
  5. washwashed with ether and ethanol
  6. customrecrystallized from ethyl acetate/ethanol

Sources & evidence

ORD record
ord-15046e4c0c3d4e8c996d065146f8ff18
Source dataset
uspto-grants-1994_04
Patent number
US05306789

Reaction notes

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