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Suzuki-Miyaura Cross-Coupling of phenylboronic acid and 4-bromochlorobenzene; 4-chloro-1,1'-biphenyl

SyntheticPage 822
Submitted Jun 14, 2017, published Jun 15, 2017
Steven M. Kennedy (Steven.Kennedy@millersville.edu), Gloria S. Chung (gschung@millersville.edu), Michael D. Buell (mdbuell@millersville.edu)
A contribution from Kennedy Group, Millersville University


			Reaction Scheme: Suzuki-Miyaura Cross-Coupling of phenylboronic acid and 4-bromochlorobenzene

Chemicals Used

1-Bromo-4-chlorobenzene (99%, TCI America)
Phenylboronic acid (98% Combi-Blocks)
Palladium atomic absorption standard solution, 1,000 μg/mL Pd in 5% HCl (Sigma-Aldrich)
95% Ethanol
1M Potassium hydroxide in water
Dichloromethane (DCM)
Dimethyl sulfone (DMSO2, a Standard for quantitative NMR, TraceCERT®, Sigma-Aldrich)

Procedure

Open to air, in a 25 mL round bottom flask, 4-bromochlorobenzene (0.189 g, 1.0 mmol) was completely dissolved in 8 mL of 95% ethanol by rapid magnetic stirring; next, phenylboronic acid (0.128 g, 1.05 mmol) was added, followed by 2 mL of 95% ethanol. The palladium standard solution (approx. 0.2 mL) was added via a 1 mL syringe. The resulting solution was stirred for 3 minutes before 2 mL of 1 M potassium hydroxide solution was added. The reaction mixture was stirred rapidly at room temperature for 25 minutes; at which time, ice cold water (5 mL) was added. After collection via vacuum filtration, the solid crude product was washed with ice-cold water (2 mL). The crude product was dissolved in DCM (2 mL); then, the solution was passed through a plug of anhydrous magnesium sulfate using an additional 4 mL of DCM. The NMR internal standard (IS), dimethyl sulfone (0.047 g, 0.5 mmol), was added to the DCM solution (approx. 6 mL). The DCM was removed via rotory evaporation to yield 4-chloro-1,1'-biphenyl as a white powder (0.12 g, 0.64 mmol, 64% isolated yield, 58% yield based on IS).

Author's Comments

Additon of the NMR internal standard (DMSO2) is optional; the DMSO2 has a 1H NMR chemical shift of 2.99 ppm and a 13C NMR chemical shift of 42.66 ppm. This is a very nice reaction for the undergraduate laboratory. The lead reference (Hill and Leadbeater) has many other examples that are higher yielding. The additional reference (Molander and Cavalcanti) contains more characterization data for the title compound.

Data

1H NMR (400 MHz, CDCl3): 7.57-7.55 (m, 2H), 7.52 (d, 2H), 7.46-7.43 (m, 2H), 7.41 (d, 2H), 7.38-7.35 (m, 1H).
13
C NMR (100 MHz, CDCl3): 139.96, 139.64, 133.34, 128.90, 128.87, 128.38, 127.58, 126.97.  

Lead Reference

N.J. Hill, M.D. Bowman, B.J. Esselman, S.D. Byron, J. Kreitinger, N.E.Leadbeater, J. Chem. Educ. 2014, 91, 1054

Other References

G.A. Molander, L.N. Cavalcanti, J. Org. Chem. 2011, 76, 7195.

Supplementary Information

13C_NMR_Full_4-chloro-1,1'-bip (CNMR_Full.pdf)
13C_NMR_Zoom_4-chloro-1,1'-bip (CNMR_Zoom.pdf)
1H_NMR_Full_4-chloro-1,1'-biph (HNMR_Full.pdf)
1H_NMR_Zoom_4-chloro-1,1'-biph (HNMR_Zoom.pdf)

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Get structure file (.cdx, .sk2, .mol)

Keywords: aromatics/arenes, ligand-free, organometallics, palladium

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