1-(4-Iodophenyl)ethan-1-one → 4-Acetylbiphenyl

HRID 2227876Notes

Reaction equation

HRID 2227876 reaction equation
I[C:2]1[CH:7]=[CH:6][C:5]([C:8](=[O:10])[CH3:9])=[CH:4][CH:3]=1>CCCC[N+](CCCC)(CCCC)CCCC.C1C=CC([Si-](F)(F)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CN(C=O)C.[CH2-]C=C.[CH2-]C=C.Cl[Pd+].Cl[Pd+]>[C:8]([C:5]1[CH:6]=[CH:7][C:2]([C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)=[CH:3][CH:4]=1)(=[O:10])[CH3:9]

Participants

5

Reactant 1

HCID 728691-(4-Iodophenyl)ethan-1-one

Product 1

HCID 71134-AcetylbiphenylYield 174%

Reagents, catalysts & solvents 3

HCID 61538Palladium, di-mu-chlorobis(eta3-2-propenyl)di-CatalystHCID 9893474Tetrabutylammonium DifluorotriphenylsilicateCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
95 °C

Procedure

To a solution of 0.101 g (0.410 mmol) of 4′-iodoacetophenone and 1.113 g (2.062 mmol) of TBAT in 10 mL of DMF was added 12 mg (0.033 mmol) of allyl palladium chloride dimer. The reaction mixture was degassed to remove oxygen via one freeze-pump-thaw cycle. The red-brown mixture was heated at 95° C. for 5 h. The resulting brown mixture was quenched by the addition of 50 mnL of H2O; the aqueous layer was then extracted with 4×50 mL of Et2O, and the combined organic layers were dried over MgSO4 and concentrated in vacuo. Purification of the residue by flash chromatography (25 mm, 17 cm, 0-10% EtOAc/hexane) gave 70 mg (86%) of 4-acetylbiphenyl as a yellow solid and 7 mg 14%) of 4,4′-diacetylbiphenyl, the homocoupled product. Recrystallization from absolute EtOH yielded pale yellow needles: TLC Rf=0.29 (10% EtOAc/hexane); mp 119-119.5° C. (lit. mp 119-120° C. (EtOH) Echavarren, A. M. and Stille, J. K., J. Am. Chem. Soc. 109:5478-5486 (1987)); IR (CCl4) 3081 (w), 3038 (w), 3000 (w), 2931 (m), 2850 (w), 1691 (m), 1569 (s), 1538 (s); 1H NMR δ2.63 (s, 3H), 7.88 (t, J=7.3, 1H), 7.46 (t, J=7.4, 2H), 7.61 (d, J=7.2, 2H), 7.67 (A of AB quartet, JAB=8.4, 2H), 8.02 (B of AB quartet, JAB=8.4, 2H); 13C NMR δ26.6, 127.2, 128.2, 128.9, 135.9, 139.9, 145.8, 197.7; LRMS (EI) 197 ((M+1), 10), 196 ((M+), 59), 181 (100), 158 (35), 152 (41); HRMS (EI) calcd for C14H12O 196.0888 (M+); found 196.0883. The IR and 1H NMR are identical to the spectral reported by Echavarren and Stille.

Workup

  1. customThe reaction mixture was degassed
  2. customto remove oxygen via one freeze-pump-thaw cycle
  3. customThe resulting brown mixture was quenched by the addition of 50 mnL of H2O
  4. extractionthe aqueous layer was then extracted with 4×50 mL of Et2O
  5. dry with materialthe combined organic layers were dried over MgSO4
  6. concentrationconcentrated in vacuo
  7. customPurification of the residue by flash chromatography (25 mm, 17 cm, 0-10% EtOAc/hexane)

Sources & evidence

ORD record
ord-8bd540fa98484985bf4188d005af665b
Source dataset
uspto-grants-2002_07
Patent number
US06414173B1

Reaction notes

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