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Cara Carter CHEM 3611L

Nucleophilic Aromatic Substitution

Nucleophilic aromatic substitution occurs daily in our lives. Though we may be unaware of it, nucleophilic aromatic substitution is constantly being conducted in industry to create certain chemicals and materials [1], in nature and even the human body. Nucleophilic aromatic substitution is one of those simple yet complex things that enable us to continue our existence. It is simple because it is not a difficult concept to grasp. It is complex because there are very important details that could determine whether one truly understands the concept of nucleophilic aromatic substitution. In order to discuss this topic in detail it is imperative to first give some definitions, explain ipso substitution, explain substitution of simple haloarenes and exceptions to the rules learned in the aforementioned topics. Let us begin. The first definition we must know is aromatic because, after all, if we are unsure that something is aromatic we cannot be sure it undergoes aromatic substitution. In order to be aromatic a compound must have a constant pi election cloud with an odd number of pi electron pairs, be planar and cyclic. If a compound does not possess all three of these characteristics it is not an aromatic structure [2]. An example of such a compound is a benzene ring. Benzene rings will be what we use to further discuss the concepts in this article. We must also know what a nucleophile is. A nucleophile is an ion or molecule that can donate electrons. Nucleophiles tend to be oxidizing agents [3]. Resonance structures are also important components of the subject. A resonance structure is one possible structure of a molecule. When all resonance structures are considered together they form a resonance
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Cara Carter CHEM 3611L

hybrid [3]. Which leads us into resonance stabilization. Resonance stabilization is extra stability a compound gains when it has delocalized electrons [2]. Other important definitions include ortho-, meta- and para-. As we know from general chemistry and organic chemistry I, each carbon in a structure has a position or number. Ortho- ,meta- and para- are used to describe the location of substituents on a benzene ring. Ortho- describes a benzene ring whose substituents are attached at positions 1&2. Likewise, meta- and para- describe benzene rings whose substituents are attached at 1&3 and 1&4 respectively. A common concept in this topic is ipso substitution. Ipso is Latin for on itself. A ipso substitution occurs when a nucleophile replaces a halogen on an aromatic structure. The aforementioned transformation is referred to as simply a nucleophilic aromatic substitution. An ipso substitution is most successful when at least one strong electron-withdrawing group is related to the leaving group by and ortho- or para- relationship. This type of reactions takes place in two steps: 1. Nucleophilic Addition 2. Leaving Group Elimination. The nucleophilic addition step is aided in large part by resonance stabilization. The leaving group elimination step is relies on resonance stabilization [1]. It is the rearrangement of the structures delocalized ions that cause the leaving group to leave. Nucleophilic aromatic substitution of simple haloarenes is much like the process explained previously. A haloarene is a benzene ring whose only substituent is a halogen. These follow a two step process as well: 1. Elimination 2. Addition. In the elimination step, a phenol anion is produced followed by a benzyne intermediate. This benzyne intermediate is
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Cara Carter CHEM 3611L

highly reactive. The addition step is just what its name implies, the addition of the nucleophile [1]. After the nucleophile is added resonance stabilization occurs. As with anything in nature, there is always something that is different than what is normally accepted. Nucleophilic aromatic substitution of simple haloarenes is no different. At high temperatures and pressures some haloarenes produce products which include a structure with a benzene ring and a salt. Consider chlorobenzene when reacted with sodium hydroxide and an abundance of water and H+ ions at 340OC and 150 atm. This particular reaction will produce phenol and sodium chloride. Following the same form, chlorobenzene when reacted with potassium amide, ammonia and an abundance of water and H+ ions at high temperature and pressure, produces potassium chloride and aniline [1]. A very interesting thing happens when radioactive chlorobenzene (14C) is used in a nucleophilic aromatic substitution reaction. When radioactive chlorobenzene is reacted with potassium amide, aqueous ammonia, an abundance of water and H+ ions at high temperature and pressure, and potassium chloride is substracted, 1,2-benzenamine-14C and benzenamine2-14C are produced. Until this point there has only been one product possibility, however, radioactive materials follow different rules and thus are able to produce more than one product [1]. Though this is not everything concerning nucleophilic aromatic substitution, these are very important and basic concepts that must be mastered in order to adequately understand the topic. A lot of this information may seem unimportant but consider this: You have left materials in a lab overnight. When you left the night before, the chemicals were separated
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Cara Carter CHEM 3611L

into benzene, halogens and other chemicals. A very mild earthquake occurs throughout the night and causes things to fall off shelves and react with other chemicals. When you return to the lab in the morning you must properly dispose of these chemicals, except you do not know what the chemicals are. You use NMR to determine what bonds exist and become curious as to how a certain chemical was created. How do you determine the process? Of course you would use retrosynthesis but if you do not know how to conduct a nucleophilic aromatic substitution reaction you will not be able to determine this. Sure that seems extreme but in the laws of nature anything can happen. After all, as Whitney Young, Jr. once said, Its better to be prepared for an opportunity and not have one that to have an opportunity and not be prepared. Chemistry may not seem like an opportunity but we must remember that science is the only opportunity that has afforded us life daily and it is the only opportunity to continue to sustain us and the generations to come.

Cara Carter CHEM 3611L References 1. Vollhardt, K., P. & Schore, N. E.(Eds.). (2003). Organic Chemistry Structure and Function. New York,NY: W.H. Freeman and Company. 2. Bruice, P. Y. (2007). Organic Chemistry. Upper Saddle River, NJ: Pearson Prentice Hall. 3. Daintith, J. (2008). A Dictionary of Chemistry. Place: Oxford University Press.