Iodine → 4-[(4-Chlorophenyl)ethynyl]benzaldehyde

HRID 1454437Notes

Reaction equation

HRID 1454437 reaction equation
N#N.[Mg].Br[C:5]1[CH:10]=[CH:9][C:8]([C:11]#[C:12][C:13]2[CH:18]=[CH:17][C:16]([Cl:19])=[CH:15][CH:14]=2)=[CH:7][CH:6]=1.II.[CH:22](N1CCCCC1)=[O:23]>C1COCC1>[Cl:19][C:16]1[CH:17]=[CH:18][C:13]([C:12]#[C:11][C:8]2[CH:9]=[CH:10][C:5]([CH:22]=[O:23])=[CH:6][CH:7]=2)=[CH:14][CH:15]=1

Participants

7

Reactant 5

HCID 807IodineHCID 947Nitrogen2×HCID 174291-PiperidinecarboxaldehydeHCID 5462224MagnesiumHCID 575306151-Bromo-4-[(4-chlorophenyl)ethynyl]benzene2×

Product 1

HCID 112534834-[(4-Chlorophenyl)ethynyl]benzaldehydeYield 318.6%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

To a dry 100 mL three-necked flask under a flow of N2 containing magnesium turnings (0.595 g; 24.50 mmol) in dry THF (10 mL) at reflux, an activating, small amount of 1-bromo-4-[(4-chlorophenyl) ethynyl] benzene (VIId) (0.39 g; 1.33 mmol) was added in one portion. N2 flow and stirring were stopped. Reaction mixture was heated at reflux for 5 minutes then iodine crystal was added keeping vigorous reflux to start the reaction. The reaction mixture went colourless after 5minutes and reaction mixture turned black-blue after an additional minute. A solution of the remaining amount of 1-bromo-4-[(4-chlorophenyl) ethynyl] benzene (VIId) (6.104 g; 20.93 mmol) in dry THF (35 mL) at 55° C. was added drop wise into the reaction mixture while keeping gentle reflux. Reflux was maintained for 15minutes then temperature was allowed to cool to RT under stirring for 1 h. The reaction mixture was cooled to 3° C. and a solution of dry 1-formyl-piperidine (3.71 mL; 33.40 mmol) in dry THF (10 mL) was added drop wise maintaining temperature at 5° C. The reaction mixture was then allowed to warm to RT and it was stirred overnight. Protocol and work-up was then similar with those described above. Purification was performed by flash chromatography (SiO2) using (cyclohexane 9-ethyl acetate 1). The title compound (m=1.02 g) was obtained as a white solid in a19% yield. Melting point: 164° C.

Workup

  1. temperatureat reflux
  2. customReaction mixture
  3. temperaturewas heated
  4. temperatureat reflux for 5 minutes
  5. temperaturekeeping vigorous reflux
  6. customthe reaction
  7. customreaction mixture
  8. temperatureReflux
  9. temperaturewas maintained for 15minutes
  10. temperatureThe reaction mixture was cooled to 3° C.
  11. temperaturewise maintaining temperature at 5° C
  12. temperatureto warm to RT
  13. stirringit was stirred overnight
  14. customPurification

Sources & evidence

ORD record
ord-67bbbc4c374c454bb02ec4f109814b96
Source dataset
uspto-grants-2009_01
Patent number
US07479575B2

Reaction notes

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