4-Iodobenzaldehyde → 1-(4-Ferrocenylphenyl)-2-(4-formylphenyl)acetylene

HRID 1824644Notes

Reaction equation

HRID 1824644 reaction equation
[C:1]([C:3]1[CH:8]=[CH:7][C:6]([C-:9]2[CH:13]=[CH:12][CH:11]=[CH:10]2)=[CH:5][CH:4]=1)#[CH:2].[CH-:14]1[CH:18]=[CH:17][CH:16]=[CH:15]1.[Fe+2:19].I[C:21]1[CH:28]=[CH:27][C:24]([CH:25]=[O:26])=[CH:23][CH:22]=1>[Cu]I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[C-:9]1([C:6]2[CH:7]=[CH:8][C:3]([C:1]#[C:2][C:21]3[CH:28]=[CH:27][C:24]([CH:25]=[O:26])=[CH:23][CH:22]=3)=[CH:4][CH:5]=2)[CH:13]=[CH:12][CH:11]=[CH:10]1.[CH-:14]1[CH:18]=[CH:17][CH:16]=[CH:15]1.[Fe+2:19]

Participants

5

Reactant 2

HCID 966574-IodobenzaldehydeHCID 12983857p-Ferrocenylphenylacetylene

Product 1

HCID 1317257561-(4-Ferrocenylphenyl)-2-(4-formylphenyl)acetylene

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalyst

Procedure

Samples of 4 (500 mg, 1.75 mmol), 4-iodobenzaldehyde (406 mg, 1.75 mmol), CuI (18 mg, 94 μmol) and Pd(PPh3)2Cl2 (8 mg, 11 μmol) were placed in a Schlenk flask. The flask was evacuated for 3 min and then the flask was backflushed with argon for 3 min. The process of evacuation and flushing was repeated 3 times. At this point flow rate was increased and the threaded stopcock was removed. Deaerated THF (5 mL) and DIEA (5.0 mL) were added in succession to the flask by gas-tight syringe. The threaded stopcock was replaced, the argon flow rate was reduced and the flask was immersed in an oil bath thermostated at 40° C. The reaction was stopped after 40 h. The mixture was then evaporated and the resulting orange solid was chromatographed (silica, CH2Cl2/hexanes, 1:1). The second orange band comprising the title compound was collected (579 mg, 84.9%). mp 219–220° C.; 1H NMR δ 4.10 (s, 5H), 4.42 (s, 2H), 4.73 (s, 2H), 7.52 (s, 4H), 7.72, 7.92 (AA′BB′, 4H), 10.07 (s, 1H); 13C NMR δ 67.3, 70.3, 70.5, 84.6, 89.4, 94.8, 120.2, 126.6, 130.4, 130.6, 132.6, 132.7, 135.9, 141.6, 192.2; EI-MS obsd 390.0696 (M+), calcd exact mass 390.0707; Anal. Calcd for C25H18FeO: C, 76.94; H, 4.65; Found: C, 76.75; H, 4.68.

Workup

  1. customThe flask was evacuated for 3 min
  2. customThe process of evacuation and flushing
  3. temperatureAt this point flow rate was increased
  4. customthe threaded stopcock was removed
  5. additionDeaerated THF (5 mL) and DIEA (5.0 mL) were added in succession to the flask by gas-tight syringe
  6. customthe flask was immersed in an oil bath
  7. customat 40° C
  8. waitThe reaction was stopped after 40 h
  9. customThe mixture was then evaporated
  10. customthe resulting orange solid was chromatographed (silica, CH2Cl2/hexanes, 1:1)
  11. customwas collected (579 mg, 84.9%)

Sources & evidence

ORD record
ord-cee222d0cba74449ac33a4abbd89e39f
Source dataset
uspto-grants-2006_05
Patent number
US07042755B1

Reaction notes

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