Greening Up the Suzuki Reaction

Calculations: phenylobronic acid 121.93g/mole = 0.0018453210858689

4-iodophenol 220.01 g/mole

= 0.001515385664288, 4-iodophenol limiting reactant 0.001515385664288 + 0.0018453210858689 = 0.0033607067501569 mol product 0.0033607067501569mole 4-phenylphenol molecular weight = 170.21g/mole % error in yield . = 83.35% error = .50647grams

Objective: The Suzuki reaction is a coupling reaction utilizing boronic acid and a halide catalyzed by Palladium. It was first established in 1979 by Akira Suzuki. The Suzuki reaction involves carbon cross-coupling and these reactions are among the most important processes in organic chemistry. They are considered fundamental building blocks in pharmaceutical and countless other chemical fields. The bond is formed with a carbon to carbon single bond coupled by an organoboron species with a halide using palladium as a catalist. The Suzuki reaction process allows us to quickly and easily couple two compounds together using a minimal amount of the palladium catalyst.

Summery: Yield Theoretical Yield % error Melting Point .27623g .50647 83.35% 170-173oC

The idea behind the Suzuki reaction is very strait forward, we can join two chains of carbon groups together, provided they are organoboron species (R1-BY2) and a halide(R2-X) using a palladium catalyst and as a base.

(image source: Zhang, YuHong(2005))

(image source: Zhang, YuHong(2005))

Oxidative addition occurs when a metal inserts itself into an X Y bond, which is then broken when the metal inserts into it forming a YMX species. This reaction is an oxidation reaction because the metals oxidation state increases by 2. Transmetallatio n occurs when the organo boronic acid acting as nucleophile swaps the R group with the halide on Pd. Reductive elimination is the exact opposite of oxidative addition.( Zhang, Y 2005)

The image above depicts the mechanism of the Suzuki reaction, which I like better than our lab manuals because it is simplified and more conducive to what we did in a green

reaction. The first step of any Suzuki reaction being oxidative addition of palladium to the halide, in our case 4-iodophenol to form the organopalladium compound, reaction with the potassium carbonate gives intermediate. Then during the transmetalation phase with phenylboronic acid we form the organopalladium compound. During reductive elimination we have our desired product 4-Phenylphenol and the palladium catalyst having been cleaved, is free to restart the catalytic cycle once again. Its important to note the necessity of a base, in our case potassium carbonate and how at the time this reaction was developed it wasnt fully understood. The base was first believed to form a trialkyl borate, in the case of a reaction of an trialkylborane and alkoxide. In the refrenced material above they used quotations to indicate the boronic acid acted like a nucleophile, this is because its not a true nucleophile; only that its more nucleophilic, as such its more reactive towards the palladium present in transmetalation. When the role of the base in the reaction mechanism for the Suzuki coupling was investigated they found that the base has three roles: Formation of the palladium complex [ArPd(OR)L2], formation of the trialkyl borate and the acceleration of the reductive elimination step by reaction of the alkoxide with the palladium complex. ( oln r, . 2 ) As it turns out the activation of the boron atom enhances the polarisation of the organic ligand, only facilitating transmetallation. By understanding the mechanism of polarization different catalysts have been utilized other than the original palladium catalyst, which opens the door for different types of Suzuki reactions, such as the Suzuki-Miyaura reaction. The Suzuki-Miyaura reaction can involve a nickel catalyst, thusly named because the first nickel catalyzed cross-coupling reaction was reported by Miyaura in 1996 (skalfdlslkajdflljkadlkfdsallksdf) using aryl chlorides and boronic acids. As nickel is much a much cheaper to work with when compaired to palladium, its gained significant notoriety and is sure to be a favorable when doing a cost analysis when performing a labritory expairment. Many sources of error could have occurred during this experiment. Not being able to correctly weight such a small amount of palladium could have given us a huge error in formulating how much product we should have obtained. Even though the limiting reactant was phenylboronic acid, if we didnt use enough of the catalyst we wouldnt have produced meaningful results during the short time refluxed. Improper calibration of the scale would also have made a substantial difference, seeing how we used very small amounts of our base, potassium carbonate and our palladium catalyst. Other sources of mechanical errors could have occurred from an inadequate amount of base being used, as we know it is an integral part to the suziki reaction cycle. For this particular lab I obtained a substandard yield, .27623g, which is horrible. When I think back as to what could have been the cause of such a low yield I keep coming back to the step where my product is dissolved into methanol via a heat source, then placed on an ice-bath to recrystallize. Before I dissolved my product into the methonal and placed it on the heating mantle I had three times more product, but after it was dissolved it never recrystallized to the same mass, which doesnt make any sense because I left it in the ice bath for over fortyfive minutes; which is ample time for the product to emerge. None of the other lab participants made it to that step, I wish I could have compared their results before and after

the ice bath, because Im convinced something was wrong with that final step that absorbed my product. If given the chance to do it again, I would put a magnetic stir bar into the solution just to insure everything had a chance to mix properly; because Im convinced it was that step that contributed to such a disgraceful yield. Although my melting point was conducive to the melting point of 4-Phenylphenol, 165oC, my melting point of 173oC isnt exact; its safe to assume I successfully synthesized a relatively pure product, but, there is room for improvement.

Conclusion: All in all this was an enjoyable experiment, it wasnt complicated, the concept was easy to understand and the applications for such a versatile reaction will most certainly come in handy if I were to peruse a job in the chemical field. Also, as stated earlier the Suzuki reaction is becoming more commonplace with less exotic and expensive materials, such as nickel, which will undoubitly further its popularity for industrial applications. I also think its cool that now whenever someone mentions a particular type of car or motorcycle I have a reason to bring up a chemistry topic and tell them a little something about how a chemical principal they have never heard of fuels the creation of future products, just as much as gas fuels their car.

I pledge this work is my own and I received no unauthorized help with the creation of this material.

_______________________________ Signature

____________________ Date

References:

Carroll Community College (2011). Organic Chemistry Laboratory Manual. Westminster, Maryland. McMurry, John. Organic chemistry. 8th. ed. Australia: Brooks/Cole Cengage Learning, 2012. Print. Sciencelab.com, Inc. (2005, October 9). Material Safety Data Sheet Phenylbronic acid MSDS. Retrieved from http://www.sciencelab.com/msds.php?msdsId=823954 Sciencelab.com, Inc. (2005, October 10). Material Safety Data HCL MSDS. Retrieved from http://www.sciencelab.com/msds.php?msdsId=9926060 Sciencelab.com, Inc. (2005, October 10). Material Safety Data Sheet Palladium
MSDS. Retrieved from http://www.sciencelab.com/msds.php?msdsId=9927393

Sciencelab.com, Inc. (2005, October 10). Material Safety Data Sheet iodophenol
MSDS. Retrieved from http://www.sciencelab.com/msds.php?msdsId=5412365

Palladium-catalyzed coupling reactions practical aspects and future developments. Weinheim, Germany: Wiley-VCH. Zhang, YuHong, Liu, Leifang, Wang, Yanguang. Water-Promoted Suzuki Reaction in Room Temperature Ionic Liquids. Synlett 2005 Retrieved from: http://www.chm.uri.edu/bdeboef/chm292/water-promoted-suzuki-reaction.pdf