CHM 313

The Suzuki-Miyaura reaction: Synthesis of 4-nitro-1,1'-biphenyl

Reaction:

Chemicals required:

1-bromo-4-nitrobenzene, phenylboronic acid, Palladium (5% on Carbon), sodium carbonate, ethanol.

Glassware & Equipment required:

15 mL Schlenk tube, syringes, measuring cylinders, spatula, sample vials, melting point apparatus, melting point
capillary, TLC jar, TLC capillaries, TLC plates, ice-bath, glass rod, magnetic stirrer, magnetic stir-bar, glass
droppers, forceps, B-14 septum.

Hazards information: For material safety data sheet (MSDS) consult the lab in-charge.

1-bromo-4-nitrobenzene: Toxic if swallowed or inhaled. May lead to cyanosis. Danger of cumulative effects.
Eye irritant, inflammation of the eye is characterized by redness, watering, and itching.

Phenylboronic acid: Causes eye irritation. Causes skin irritation. Harmful if swallowed. May cause irritation of
the digestive tract. Causes respiratory tract irritation. May be harmful if inhaled.

Palladium (5% on Carbon): Flammable solid. May cause eye, skin, and respiratory tract irritation.

Ethanol: Vapors are highly flammable and can produce CNS depression, eye and upper respiratory tract
irritation. Symptoms may include burning sensation, headache, dizziness, tremors, nausea and other symptoms
similar to ingestion. Ingestion results in dose-related central nervous system depression, ranging from inebriation
to anesthesia, narcosis, coma, respiratory failure, and death in significant exposures. Symptoms include
headaches, tremors, fatigue, hallucinations, distorted perceptions, and convulsions.
Precautions: Use lab-coat, safety goggles and gloves at all time in the lab. Handling of chemicals and reaction
should be carried in a fume hood. Never touch, smell or taste the chemicals. For more details read MSDS of
chemicals which you are using. Any accident should be promptly informed to the instructor.

Procedure: (This reaction is to be performed on 200 mg scale of 1-bromo-4-nitrobenzene)

Take 1 equivalent of 1-bromo-4-nitrobenzene in a Schlenk tube fitted with a nitrogen balloon and stopper the
neck with a septum. Add 1.5 equivalent of phenylboronic acid and 3.5 equivalent of Na2CO3. Add a magnetic
stir-bar. Add 5 mL of EtOH and stir well. Degas the solution by bubbling Argon. Add 3.5 mol% of 5%
palladium on carbon (weighed in an eppendorf tube). Allow the reaction to stir for overnight at RT. Check a
TLC by spotting the reaction mixture directly. Compare with the starting material. If the reaction is complete,
filter it carefully using a fluted filter paper (Whatman) and wash the residue with EtOH. Concentrate the filtrate
under reduced pressure. Depending upon the polarity of your TLC, perform a silica gel column chromatography
to purify the product. Record the yield and transfer the purified product to a sample vial and label it. Record an
IR spectrum for the purified product.

Note down all the observations in your lab notebook. Clean all your glassware and hand them over to the
lab attendant.

Questions:

 Write down the mechanism of the reaction

 What bands will you look for in the IR spectrum of the product?

 What are other ways of synthesizing the same product?

 Will the product show atropisomerism?