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

HRID 1454433Notes

Reaction equation

HRID 1454433 reaction equation
N#N.[Mg].II.Br[C:7]1[CH:12]=[CH:11][C:10]([C:13]#[C:14][C:15]2[CH:20]=[CH:19][C:18]([CH2:21][CH3:22])=[CH:17][CH:16]=2)=[CH:9][CH:8]=1.[CH:23](N1CCCCC1)=[O:24]>C1COCC1.BrC1C=CC(C#CC2C=CC(CC)=CC=2)=CC=1>[CH2:21]([C:18]1[CH:19]=[CH:20][C:15]([C:14]#[C:13][C:10]2[CH:11]=[CH:12][C:7]([CH:23]=[O:24])=[CH:8][CH:9]=2)=[CH:16][CH:17]=1)[CH3:22]

Participants

8

Reactant 5

HCID 807IodineHCID 947Nitrogen2×HCID 174291-PiperidinecarboxaldehydeHCID 5462224MagnesiumHCID 575306181-Bromo-4-[(4-ethylphenyl)ethynyl]benzene

Product 1

HCID 112763804-[(4-Ethylphenyl)ethynyl]benzaldehydeYield 89.6%

Reagents, catalysts & solvents 2

HCID 575306181-Bromo-4-[(4-ethylphenyl)ethynyl]benzeneCatalystHCID 8028TetrahydrofuranSolvent2×

Procedure

To a dry 100 mL three-necked flask under a flow of N2 containing magnesium turnings (0.782 g; 32.17 mmol) in dry THF (10 mL) at reflux, an activating, small amount of 1-bromo-4-[(4-ethylphenyl) ethynyl] benzene (VIIc) (0.500 g; 1.75 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-green after an additional minute. A solution of the remaining amount of 1-bromo-4-[(4-ethylphenyl) ethynyl] benzene (VIIc) (7.84 g; 27.49 mmol) in dry ThF (30 mL) was added drop wise into the reaction mixture while keeping gentle reflux. Reflux was maintained for 15 minutes 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 (4.12 mL; 43.87 mmol) in dry THF (25 mL) was added drop wise maintaining temperature at 5° C. The reaction mixture was then allowed to warm to room temperature (RT) and it was stirred overnight. Protocol and work-up was then similar with those described above. The title compound (m=5.77 g) was obtained as a cream solid in a 84% yield. Melting point: 89° 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 15 minutes
  10. temperatureThe reaction mixture was cooled to 3° C.
  11. temperaturewise maintaining temperature at 5° C
  12. temperatureto warm to room temperature (RT) and it
  13. stirringwas stirred overnight

Sources & evidence

ORD record
ord-303fa5d7eb4a4a22b80dcc5cc33dda3b
Source dataset
uspto-grants-2009_01
Patent number
US07479575B2

Reaction notes

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