How green is your bromination reaction?

How green is your bromination reaction?

By Diya Zhu: Symposium Coordinator for the GCI

Electrophilic bromination is a common type of reaction in undergraduate organic laboratories. In these experiments, we rarely use Br2 as a bromine source. Why? This dense brownish-red liquid is a pain in the butt for a few reasons. First of all, it fumes. Once you open the bottle, orange fumes start migrating everywhere. Without efficient ventilation, soon you will smell an offensive and suffocating odor. Second, bromine is corrosive to human tissue as a liquid and its vapours irritate the eyes and throat. Moreover, with inhalation, bromine vapours are very toxic. Third, bromine is very dense, with a density of 3.1 g/cm3, which makes it very difficult to measure and transfer.

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Figure 1. A bottle containing bromine.1

Instead, N-bromosuccinimide (NBS) is often used as a brominating and oxidizing agent in various electrophilic addition, radical addition, and electrophilic substitution reactions. Pure NBS is a white crystalline solid with a melting point of 175-180 oC. Even though it’s a solid and easier to handle, you still need to be careful when working with NBS. Due to the higher electronegativity of nitrogen, the Br atom is partially positively charged and thus electrophilic, ready to be attacked by a nucleophile (eg. an alkene).

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Figure 2. N-bromosuccinimide (NBS)

NBS will form bromonium ions with alkenes, and when an alcohol or water is added, it will attack the bromonium ion, which will generate bromohydrins. Importantly, the nucleophilic attack only happens on the face opposite the bromonium ion.

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Figure 3. Alkene reaction with NBS showing the bromonium ion and attack of water to form a racemic mixture.

Usually, when undergraduate students preform this experiment, we also emphasized the importance of Green Chemistry. Green chemistry and its 12 principles help to improve conventional reactions. For example, increasing the efficiency of synthetic methods, reducing the steps of synthesis, and minimizing toxic reagents and solvents. In the formation of bromohydrins, compared to using Br2, NBS is less hazardous.  Also, water or alcohol can be used as the solvent which eliminates the use of organic solvents, especially chlorinated solvents.

However, the use of NBS also creates by-products. For example, succinimide and the very strong hydrobromic acid. It also has a reduced atom economy, since only one Br atom of 8 atoms in a NBS molecule is used in bromination.

With all of this taken into consideration, can it be concluded that NBS is a greener alternative to Br2? What do you think, and which reagent will you be reaching for in your next bromination experiment?

References:

  1. https://en.wikipedia.org/wiki/Bromine
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