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Naming Aromatic Compounds

Naming an organic compound requires several steps. What follows is a minimal outline. Consult your textbook for more details and examples. 1. 2. 3. 4. 5. 6. Find the longest continuous chain of carbon atoms. This longest chain may not be written in a straight line. Name that longest chain with the appropriate alkane name. Find the substituents and name each of them with the appropriate group name. Number the carbons in the chain such that the lowest number is given to the group nearest one end of the chain. List the groups alphabetically in front of the longest chain name. Precede each group name with a prefix indicating how many of them are present in the molecule. In front of the prefix, list the numbers of each group in the molecule and separate the numbers with a hyphen.

THE NAMES OF AROMATIC COMPOUNDS


This page looks at the names of some simple aromatic compounds. An aromatic compound is one which contains a benzene ring. It assumes that you are reasonably confident about naming compounds containing chains of carbon atoms (aliphatic compounds).
Note: If you aren't sure about naming aliphatic compoundsfollow this link before you go on.

Naming aromatic compounds isn't quite so straightforward as naming chain compounds. Often, more than one name is acceptable and it's not uncommon to find the old names still in use as well.

Background
The benzene ring All aromatic compounds are based on benzene, C6H6, which has a ring of six carbon atoms and has the symbol:

Each corner of the hexagon has a carbon atom with a hydrogen attached.
Note: If you don't understand this structure, it is explained in full in two pages on the structure of benzene elsewhere in this site. Following this link could well take you some time!

The phenyl group Remember that you get a methyl group, CH3, by removing a hydrogen from methane, CH4. You get a phenyl group, C6H5, by removing a hydrogen from a benzene ring, C6H6. Like a methyl or an ethyl group, a phenyl group is always attached to something else.

Aromatic compounds with only one group attached to the benzene ring
Cases where the name is based on benzene chlorobenzene This is a simple example of a halogen attached to the benzene ring. The name is self-obvious.

The simplified formula for this is C6H5Cl. You could therefore (although you never do!) call it phenyl chloride. Whenever you draw a benzene ring with one other thing attached to it, you are in fact drawing a phenyl group. In order to attach something else, you have to remove one of the existing hydrogen atoms,

and so automatically make a phenyl group. nitrobenzene The nitro group, NO2, is attached to a benzene ring.

The simplified formula for this is C6H5NO2. methylbenzene Another obvious name - the benzene ring has a methyl group attached. Other alkyl side-chains would be named similarly - for example, ethylbenzene. The old name for methylbenzene is toluene, and you may still meet that.

The simplified formula for this is C6H5CH3. (chloromethyl)benzene A variant on this which you may need to know about is where one of the hydrogens on the CH3 group is replaced by a chlorine atom. Notice the brackets around the (chloromethyl) in the name. This is so that you are sure that the chlorine is part of the methyl group and not somewhere else on the ring.

If more than one of the hydrogens had been replaced by chlorine, the names would be (dichloromethyl)benzene or (trichloromethyl)benzene. Again, notice the importance of the brackets in showing that the chlorines are part of the side group

and not directly attached to the ring. benzoic acid (benzenecarboxylic acid) Benzoic acid is the older name, but is still in common use - it's a lot easier to say and write than the modern alternative! Whatever you call it, it has a carboxylic acid group, -COOH, attached to the benzene ring.

Cases where the name is based on phenyl Remember that the phenyl group is a benzene ring minus a hydrogen atom - C6H5. If you draw a benzene ring with one group attached, you have drawn a phenyl group. phenylamine Phenylamine is a primary amine and contains the -NH2 group attached to a benzene ring.

The old name for phenylamine is aniline, and you could also reasonably call it aminobenzene. Phenylamine is what it is most commonly for UK-based exam purposes.
Note: In all cases where there is some possibility of alternative names, you need to know what your examiners are likely to call a particular compound. Refer to yoursyllabus and recent exam papers. If you are working to a UK-based syllabus for 16 - 8 year olds, and haven't got these, follow this link to find out how to get hold of them.

phenylethene This is an ethene molecule with a phenyl group attached. Ethene is a two carbon chain with a carbon-carbon double bond. Phenylethene is therefore:

The old name for phenylethene is styrene - the monomer from which polystyrene is made. phenylethanone This is a slightly awkward name - take it to pieces. It consists of a two carbon chain with no carbon-carbon double bond. The oneending shows that it is a ketone, and so has a C=O group somewhere in the middle. Attached to the carbon chain is a phenyl group. Putting that together gives:

phenyl ethanoate This is an ester based on ethanoic acid. The hydrogen atom in the -COOH group has been replaced by a phenyl group.

Note: If you aren't happy about naming esters, follow this link before you go on.

phenol Phenol has an -OH group attached to a benzene ring and so has a formula C6H5OH.

Aromatic compounds with more than one group attached to the benzene ring
Numbering the ring Any group already attached to the ring is given the number 1 position. Where you draw it on the ring (at the top or in any other position) doesn't matter - that's just a question of rotating the molecule a bit. It's much easier, though, to get in the habit of drawing your main group at the top. The other ring positions are then numbered from 2 to 6. You can number them either clockwise or anti-clockwise. As with chain compounds, you number the ring so that the name you end up with has the smallest possible numbers in it. Examples will make this clear. Some simple examples Substituting chlorine atoms on the ring Look at these compounds:

All of these are based on methylbenzene and so the methyl

group is given the number 1 position on the ring. Why is it 2-chloromethylbenzene rather than 6chloromethylbenzene? The ring is numbered clockwise in this case because that produces a 2- in the name rather than a 6-. 2 is smaller than 6.
Warning! You will find all sorts of variations on this depending on the age of the book you look it up in, and where it was published. What I have described above isn't in strict accordance with the most modern interpretation of the IUPAC recommendations for naming organic compounds. The names should actually be 1-chloro-2-methylbenzene, 1chloro-3-methylbenzene, and so on. The substituted groups are named in alphabetical order, and the "1" position is assigned to the first of these - rather than to the more logical methyl group. This produces some silly inconsistencies. For example, if you had the exactly equivalent compounds containing nitro groups in place of the chlorines, the names would change completely, to 1-methyl-2-nitrobenzene, 1-methyl-3-nitrobenzene, etc. In this case, the normal practice of naming the hydrocarbon first, and then attaching other things to it has been completely wrecked. Do you need to worry about this? NO! It is extremely unlikely that you would ever be asked to name these in an exam, and it is always easy to write a structure from one of these names however illogical it may be! There is a simple rule for exam purposes. Unless you are specifically asked for the name of anything remotely complicated, don't give it. As long as you have got the structure right, that's all that matters.

2-hydroxybenzoic acid This might also be called 2-hydroxybenzenecarboxylic acid. There is a -COOH group attached to the ring and, because the name is based on benzoic acid, that group is assigned the number 1 position. Next door to it in the 2 position is a hydroxy group, -OH.

benzene-1,4-dicarboxylic acid The di shows that there are two carboxylic acid groups, -COOH, one of them in the 1 position and the other opposite it in the 4 position.

2,4,6-trichlorophenol This is based on phenol - with an -OH group attached in the number 1 position on the ring. There are 3 chlorine atoms substituted onto the ring in the 2, 4 and 6 positions.

methyl 3-nitrobenzoate This is a name you might come across as a part of a practical exercise in nitrating benzene rings. It's included partly for that reason, and partly because it is a relatively complicated name to finish with! The structure of the name shows that it is an ester. You can tell that from the oate ending, and the methyl group floating separately from the rest of the name at the beginning. The ester is based on the acid, 3-nitrobenzoic acid - so start with that. There will be a benzene ring with a -COOH group in the number

1 position and a nitro group, NO2, in the 3 position. The -COOH group is modified to make an ester by replacing the hydrogen of the -COOH group by a methyl group. Methyl 3-nitrobenzoate is therefore:

Nomenclature of Benzenes
Table of Contents 1. 1. 2. 3. 2. 1. 2. 3. 1. 4. 1. 2. 5. 1. 3. 4. 5. 1. 1. Introduction 1.1. Is it cyclohexane or is it benzene? 1.2. What about Resonance? 1.3. The Formation of the Phenyl Group and its Derivatives 2. Nomenclature of Benzene Derived Compounds 2.1. Simple Benzene Naming 2.2. Ortho-, Meta-, Para- (OMP) Nomenclature for Disubstituted Benzenes 2.3. Base Name Nomenclature 2.3.1. Common vs. Systematic (IUPAC) Nomenclature 2.4. The Phenyl and Benzyl Groups 2.4.1. The Phenyl Group 2.4.2. The Benzyl Group 2.5. Commonly Named Benzene Compounds Nomenclature Summary Flowchart 2.5.1. Determination of Common and Systematic Names using Flowchart 3. Outside links 4. References 5. Practice Problems 5.1. Answer Key to Practice Questions 6. 6. Contributors Benzene, C6H6, as shown on the left, is an organic aromatic compound with many interesting properties. Unlike aliphatic (straight chain carbons) or other cyclic organic compounds, the structure of benzene (3 conjugated bonds) allows benzene and its derived products to be useful in fields such as health, laboratorial, and other applications such as rubber synthesis.

Introduction

Benzene derived products are well known to be pleasantly fragrant. For this reason, organic compounds containing benzene rings were classified as being "aromatic" (sweet smelling)amongst scientists in the early 19th century when a relation was established between benzene derived compounds and sweet/spicy fragrances. There is a misconception amongst the scientific community, however, that all aromatics are sweet smelling and that all sweet smelling compounds would have a benzene ring in its structure. This is false, since non-aromatic compounds, such as camphor, extracted from the camphor laurel tree, release a strong, minty aroma, yet it lacks the benzene ring in its structure (See figure 1). On the other hand, benzene itself gives off a rather strong and unpleasant smell that would otherwise invalidate the definition of an aromatic (sweet-smelling) compound. Despite this inconsistency, however, the term aromatic continues to be used today in order to designate molecules with benzene-like rings in their structures. For a modern, chemical definition of aromaticity, refer to sectionsAromaticity and Hckel's Rule.

Figure 1. Top-view of camphor, along with its monoterpene unit. Notice how camphor lacks the benzene ring to be "aromatic". Many aromatic compounds are however, sweet/pleasant smelling. Eugenol, for example, is extracted from essential oils of cloves and it releases a spicy, clove-like aroma used in perfumes. In addition, it is also used in dentistry as an analgesic.

Figure 2. Eugenol, an aromatic compound extracted from clove essential oils. Used in perfumes and as an analgesic. The benzene ring is labeled in red in the eugenol molecule.

Is it cyclohexane or is it benzene?
Due to the similarity between benzene and cyclohexane, the two is often confused with each other in beginning organic chemistry students.

Figure 3. Structure comparison between cyclohexane and benzene If you were to count the number of carbons and hydrogens in cyclohexane, you will notice that its molecular formula is C6H12. Since the carbons in the cyclohexane ring is fully saturated with hydrogens (carbon is bound to 2 hydrogens and 2 adjacent carbons), no double bonds are formed in the cyclic ring. In contrast, benzene is only saturated with one hydrogen per carbon, leading to its molecular formula of C6H6. In order to stabilize this structure, 3 conjugated (double) bonds are formed in the benzene ring in order for carbon to have four adjacent bonds. In other words, cyclohexane is not the same as benzene! These two compounds have different molecular formulas and their chemical and physical properties are not the same. The hydrogenation technique can be used by chemists to convert from benzene to cyclohexane by saturating the benzene ring with missing hydrogens. IMPORTANT NOTE: A special catalyst is required to hydrogenate benzene rings due to its unusual stability and configuration. Normal catalytic hydrogenation techniques will not hydrogenate benzene and yield any meaningful products.

What about Resonance?


Benzene can be drawn a number of different ways. This is because benzene's conjugated pi electrons freely resonate within the cyclic ring, thus resulting in its two resonance forms. Figure 4. The figure to the left shows the two resonance forms of benzene. The delocalized electrons are moved from one carbon to the next, thus providing stabilization energy. Ring structures stabilized by the movement of delocalized electrons are sometimes referred to as arenes.

As the electrons in the benzene ring can resonate within the ring at a fairly high rate, a simplified notation is often used to designate the two different resonance forms. This notation is shown above, with the initial three pi bonds (#1,

#2) replaced with an inner ring circle (#3). Alternatively, the circle within the benzene ring can also be dashed to show the same resonance forms (#4).

The Formation of the Phenyl Group and its Derivatives


The phenyl group can be formed by taking benzene, and removing a hydrogen from it. The resulting molecular formula for the fragment isC6H5. NOTE: Although the molecular formula of the phenyl group is C 6H5, the phenyl group would always have something attached to where the hydrogen was removed. Thus, the formula is often written as Ph-R, where Ph refers to the Phenyl group, and R refers to the R group attached to where the hydrogen was removed.

Figure 5. Figure demonstrating the removal of hydrogen to form the phenyl group. Different R groups on the phenyl group allows different benzene derivatives to be formed. Phenol, Ph-OH, or C6H5OH, for example, is formed when an alcohol (-OH) group displaces a hydrogen atom on the benzene ring. Benzene, for this very same reason, can be formed from the phenyl group by reattaching the hydrogen back its place of removal. Thus benzene, similar to phenol, can be abbreviated Ph-H, or C6H6.

Figure 7. (Left): Epigallocatechin gallate (EGCG), an antioxidant found in green teas and its extracts, is famous for its potential health benefits. The molecule is a type of catechin, which is composed of multiple phenol (labeled in red) units (polyphenols - see polycyclic aromatics). Since catechins are usually found in plant extracts, they are often referred as plant polyphenolic antioxidants. As you can see above, these are only some of the many possibilities of the benzene derived products that have special uses in human health and other industrial fields.

Nomenclature Compounds

of

Benzene

Derived

Unlike aliphatic organics, nomenclature of benzene-derived compounds can be confusing because a single aromatic compound can have multiple possible names (such as common and systematic names) be associated with its structure. In these sections, we will analyze some of the ways these compounds can be named.

Simple Benzene Naming


Some common substituents, like NO2, Br, and Cl, can be named this way when it is attached to a phenyl group. Long chain carbons attached can also be named this way. The general format for this kind of naming is: (positions of substituents (if >1)- + # (di, tri, ...) + substituent)n + benzene. For example, chlorine (Cl) attached to a phenyl group would be named chlorobenzene (chloro + benzene). Since there is only one substituent on the benzene ring, we do not have to indicate its position on the benzene ring (as it can freely rotate around and you would end up getting the same compound.)

Figure 8. Example of simple benzene naming with chlorine and NO2 as substituents.

Figure 9. More complicated simple benzene naming examples - Note that standard nomenclature priority rules are applied here, causing the numbering of carbons to switch. See Nomenclature of Organic Compounds for a review on naming and priority rules.

Ortho-, Meta-, Para- (OMP) Nomenclature for Disubstituted Benzenes


Instead of using numbers to indicate substituents on a benzene ring, ortho- (o-), meta- (m-), or para (p-) can be used in place of positional markers when there are two substituents on the benzene ring (disubstituted benzenes). They are defined as the following:

ortho- (o-): 1,2- (next to each other in a benzene ring) meta- (m): 1,3- (separated by one carbon in a benzene ring) para- (p): 1,4- (across from each other in a benzene ring) Using the same example above in figure 9a (1,3-dichlorobenzene), we can use the ortho-, meta-, para- nomenclature to transform the chemical name into m-dichlorobenzene, as shown in the figure below.

Figure 10. Transformation of 1,3-dichlorobenzene into m-dichlorobenzene. Here are some other examples of ortho-, meta-, para- nomenclature used in context:

However, the substituents used in ortho-, meta-, para- nomenclature do not have to be the same. For example, we can use chlorine and a nitro group as substituents in the benzene ring.

In conclusion, these can be pieced together into a summary diagram, as shown below:

Base Name Nomenclature


In addition to simple benzene naming and OMP nomenclature, benzene derived compounds are also sometimes used as bases. The concept of a base is similar to the nomenclature of aliphatic and cyclic compounds, where the parent for the organic compound is used as a base (a name for its chemical name. For example, the following compounds have the base names hexane and cyclohexane, respectively. See Nomenclature of Organic Compounds for a review on naming organic compounds.

Benzene, similar to these compounds shown above, also has base names from its derived compounds. Phenol (C6H5OH), as introduced previously in this article, for example, serves as a base when other substituents are attached to it. This is best illustrated in the diagram below.

Figure 14. An example showing phenol as a base in its chemical name. Note how benzene no longer serves as a base when an OH group is added to the benzene ring. Alternatively, we can use the numbering system to indicate this compound. When the numbering system is used, the carbon where the substituent is attached on the base will be given the first priority and named as carbon #1 (C 1). The normal priority rules then apply in the nomenclature process (give the rest of the substituents the lowest numbering as you could).

Figure 15. The naming process for 2-chlorophenol (o-chlorophenol). Note that 2-chlorophenol = o-chlorophenol. Below is a list of commonly seen benzene-derived compounds. Some of these mono-substituted compounds (labeled in red and green), such as phenol or toluene, can be used in place of benzene for the chemical's base name.

Figure 16. Common benzene derived compounds with various substituents.

Common vs. Systematic (IUPAC) Nomenclature


According to the indexing preferences of the Chemical Abstracts, phenol, benzaldehyde, and benzoic acid (labeled in red in Figure 16)are some of the common names that are retained in the IUPAC (systematic) nomenclature. Other names such as toluene, styrene, naphthalene, or phenanthrene can also be seen in the IUPAC system in the same way. While the use of other common names are usually acceptable in IUPAC, their use are discouraged in the nomenclature of compounds. Nomenclature for compounds which has such discouraged names will be named by the simple benzene naming system. An example of this would include toluene derivatives like TNT. (Note that toluene by itself is retained by the IUPAC nomenclature, but its derivatives, which contains additional substituents on the benzene ring, might be excluded from the convention). For this reason, the common chemical name 2,4,6-trinitrotoluene, or TNT, as shown in figure 17, would not be advisable under the IUPAC ( systematic) nomenclature. In order to correctly name TNT under the IUPAC system, the simple benzene naming system should be used:

Figure 18. Systematic (IUPAC) name of 2,4,6-trinitrotoluene (common name), or TNT. Note that the methyl group is individually named due to the exclusion of toluene from the IUPAC nomenclature.

Figure 19. The common name 2,4-dibromophenol, is shared by the IUPAC systematic nomenclature. Only substituents phenol, benzoic acid, and benzaldehyde share this commonality. Since the IUPAC nomenclature primarily rely on the simple benzene naming system for the nomenclature of different benzene derived compounds, the OMP (ortho-, meta-, para-) system is not accepted in the IUPAC nomenclature. For this reason, the OMP system will yield common names that can be converted to systematic names by using the same method as above. For example, o-Xylene from the OMP system can be named 1,2-dimethylbenzene by using simple benzene naming (IUPAC standard).

The Phenyl and Benzyl Groups


The Phenyl Group
As mentioned previously, the phenyl group (Ph-R, C6H5-R) can be formed by removing a hydrogen from benzene and attaching a substituent to where the hydrogen was removed. To this phenomenon, we can name compounds formed this way by applying this rule:(phenyl + substituent). For example, a chlorine attached in this manner would be named phenyl chloride, and a bromine attached in this manner would be named phenyl bromide. (See below diagram)

Figure 20. Naming of Phenyl Chloride and Phenyl Bromide While compounds like these are usually named by simple benzene type naming (chlorobenzene and bromobenzene), the phenyl group naming is usually applied to benzene rings where a substituent with six or more carbons is attached, such as in the diagram below.

Figure 21. Diagram of 2-phenyloctane. Although the diagram above might be a little daunting to understand at first, it is not as difficult as it seems after careful analysis of the structure is made. By looking for the longest chain in the compound, it should be clear that the longest chain is eight (8) carbons long (octane, as shown in green) and that a benzene ring is attached to the second position of this longest chain (labeled in red). As this rule suggests that the benzene ring will act as a function group (a substituent) whenever a substituent of more than six (6) carbons is attached to it, the name "benzene" is changed to phenyl and is used the same way as any other substituents, such as methyl, ethyl, or bromo.Putting it all together, the name can be derived as: 2-phenyloctane (phenyl is attached at the second position of the longest carbon chain, octane).

The Benzyl Group


The benzyl group (abbv. Bn), similar to the phenyl group, is formed by manipulating the benzene ring. In the case of the benzyl group, it is formed by taking the phenyl group and adding a CH 2 group to where the hydrogen was removed. Its molecular fragment can be written as C 6H5CH2-R, PhCH2-R, or Bn-R. Nomenclature of benzyl group based compounds are very similar to the phenyl group compounds. For example, a chlorine attached to a benzyl group would simply be called benzyl chloride, whereas an OH group attached to a benzyl group would simply be called benzyl alcohol.

Figure 22. Benzyl Group Nomenclature Additionally, other substituents can attach on the benzene ring in the presence of the benzyl group. An example of this can be seen in the figure below:

Figure 23. Nomenclature of 2,4-difluorobenzyl chloride. Similar to the base name nomenclature system, the carbon in which the base substituent is attached on the benzene ring is given the first priority and the rest of the substituents are given the lowest number order possible. Under this consideration, the above compound can be named: 2,4-difluorobenzyl chloride.

Commonly Named Benzene Compounds Nomenclature Summary Flowchart

Summary Flowchart (Figure 24). Summary of nomenclature rules used in commonly benzene derived compounds. As benzene derived compounds can be extremely complex, only compounds covered in this article and other commonly named compounds can be named using this flowchart.

Determination of Common and Systematic Names using Flowchart


To demonstrate how this flowchart can be used to name TNT in its common and systematic (IUPAC) name, a replica of the flowchart with the appropriate flow paths are shown below:

Outside links

Naming Aromatic Compounds - A good review of the concepts presented above Naming Aromatic Compounds - Functional groups and compounds formed by different functional groups Naming Aromatic Compounds - Additional practice problems are available here Aromatherapy and Aromatic Compounds Michael Faraday - Discovery of Benzene and History Wikipedia - Camphor Medicinal Uses of Camphor More on Terpenes Properties of Eugenol Benzene Aromaticity and Stability Killing with Syringes: Phenol Injections - Reminisce of the Nazi's "euthanasia" project in Auschwitz Green Tea Health Benefits - Antioxidant effects of EGCG Green Tea Nutrient EGCG Blocks Diabetes - Promoting Effects of High Fructose Corn Syrup Catechins in Green Tea - Why Catechins is Important to Your Health Phytochemicals - Catechins Wikipedia - Trinitrotoluene (TNT) IUPAC Nomenclature System and Recommendations Wikipedia - Phenyl Group Wikipedia - Benzyl Group

References
1. 2. 3. 4. 5. 6. 7. 8. 9. Nicolaou, K. C., & Montagnon, T. (2008). Molecules That Changed the World. KGaA, Weinheim: Wiley-VCH. p. 54 Pitman, V. (2004). Aromatherapy. Great Britain, UK: Nelson Thornes. p.135-136 Burton, G. (2000). Chemical Ideas. Bicester, Oxon: Heinemann. p.290-292 Vollhardt, K. P.C. & Shore, N. (2007). Organic Chemistry (5th Ed.). New York: W. H. Freeman. p. 667-669 Schnaubelt, K. (1999). Medical Aromatherapy. Berkeley, CA: Frog Books. p. 211-213 Patrick, G. L. (2004). Organic Chemistry. New York, NY: Taylor & Francis. p. 135-136 Talbott, S. M. (2002). A Guide to Understanding Dietary Supplements. Binghamton, NY: Haworth Press. p. 616-619 Lifton, R. J. (2000). The Nazi doctors. New York, NY: Basic Books. p. 255-261 Myers, R. L., & Myers, R. L. (2007). The 100 most important chemical compounds. Westport, CT: Greenwood Publishing Group. p. 281-282

Practice Problems

Q1) (True/False) The compound above contains a benzene ring and thus is aromatic. Q2) Benzene unusual stability is caused by how many conjugated pi bonds in its cyclic ring? ____

Q3) Menthol, a topical analgesic used in many ointments for the relief of pain, releases a peppermint aroma upon exposure to the air. Based on this conclusion, can you imply that a benzene ring is present in its chemical structure? Why or why not?

Q4) Q5) At normal conditions, benzene has ___ resonance structures. Q6) Which of the following name(s) is/are correct for the following compound?

a) nitrohydride benzene b) phenylamine c) phenylamide d) aniline e) nitrogenhydrogen benzene f) All of the above is correct Q7) Convert 1,4-dimethylbenzene into its common name. Q8) TNT's common name is: ______________________________ Q9) Name the following compound using OMP nomenclature:

Q10) Draw the structure of 2,4-dinitrotoluene.

Q11) Name the following compound:

Q12) Which of the following is the correct name for the following compound?

a) 3,4-difluorobenzyl bromide b) 1,2-difluorobenzyl bromide c) 4,5-difluorobenzyl bromide d) 1,2-difluoroethyl bromide e) 5,6-difluoroethyl bromide f) 4,5-difluoroethyl bromide Q13) (True/False) Benzyl chloride can be abbreviated Bz-Cl. Q14) Benzoic Acid has what R group attached to its phenyl functional group? Q15) (True/False) A single aromatic compound can have multiple names indicating its structure. Q16) List the corresponding positions for the OMP system (o-, m-, p-). Q17) A scientist has conducted an experiment on an unknown compound. He was able to determine that the unknown compound contains a cyclic ring in its structure as well as an alcohol (-OH) group attached to the ring. What is the unknown compound? a) Cyclohexanol b) Cyclicheptanol c) Phenol d) Methanol e) Bleach f) Cannot determine from the above information Q18) Which of the following statements is false for the compound, phenol? a) Phenol is a benzene derived compound. b) Phenol can be made by attaching an -OH group to a phenyl group. c) Phenol is highly toxic to the body even in small doses. d) Phenol can be used as a catalyst in the hydrogenation of benzene into cyclohexane.

e) Phenol is used as an antiseptic in minute doses. f) Phenol is amongst one of the three common names retained in the IUPAC nomenclature.

Answer Key to Practice Questions


Q1) False, this compound does not contain a benzene ring in its structure. Q2) 3 Q3) No, a substance that is fragrant does not imply a benzene ring is in its structure. See camphor example (figure 1) Q4) No reaction, benzene requires a special catalyst to be hydrogenated due to its unusual stability given by its three conjugated pi bonds. Q5) 2 Q6) b, d Q7) p-Xylene Q8) 2,4,6-trinitrotoluene Q9) p-chloronitrobenzene

Q10) Q11) 4-phenylheptane Q12) a Q13) False, the correct abbreviation for the benzyl group is Bn, not Bz. The correct abbreviation for Benzyl chloride is Bn-Cl. Q14) COOH Q15) True. TNT, for example, has the common name 2,4,6-trinitrotoluene and its systematic name is 2-methyl-1,3,5trinitrobenzene. Q16) Ortho - 1,2 ; Meta - 1,3 ; Para - 1,4

Q17) The correct answer is f). We cannot determine what structure this is since the question does not tell us what kind of cyclic ring the -OH group is attached on. Just as cyclohexane can be cyclic, benzene and cycloheptane can also be cyclic. Q18) d

Benzene Derivatives

Benzene Derivatives
The nomenclature of substituted benzene ring compounds is less systematic than that of the alkanes, alkenes and alkynes. A few mono-substituted compounds are named by using a group name as a prefix to "benzene", as shown by the combined names listed below. A majority of these compounds, however, are referred to by singular names that are unique. There is no simple alternative to memorization in mastering these names.

Two commonly encountered substituent groups that incorporate a benzene ring are phenyl, abbreviated Ph-, and benzyl, abbreviated Bn-. These are shown here with examples of their use. Be careful not to confuse a phenyl (pronounced fenyl) group with the compound phenol (pronounced feenol). A general and useful generic notation that complements the use of Rfor an alkyl group is Ar- for an aryl group (any aromatic ring).

When more than one substituent is present on a benzene ring, the relative locations of the substituents must be designated by numbering the ring carbons or by some other notation. In the case of disubstituted benzenes, the prefixes ortho, meta & para are commonly used to indicate a 1,2- or 1,3- or 1,4- relationship respectively. In the following examples, the first row of compounds show this usage in red. Some disubstituted toluenes have singular names (e.g. xylene, cresol & toluidine) and their isomers are normally designated by the ortho, meta or para prefix. A few disubstituted benzenes have singular names given to specific isomers (e.g. salicylic acid & resorcinol). Finally, if there are three or more substituent groups, the ring is numbered in such a way as to assign the substituents the lowest possible numbers, as illustrated by the last row of examples. The substituents are listed alphabetically in the final name. If the substitution is symmetrical (third example from the left) the numbering corresponds to the alphabetical order.

Practice Problems
Seven questions concerning nomenclature are presented here.

Nomenclature

Now let's deal with how to name simple aromatic compounds. Aromatic compounds are what we call compounds derived from benzene. Actually, as noted earlier, that is too narrow a definition for aromatic compounds but it will serve for this course.

Examples At this point I need to introduce a new functional group, one that we have not dealt with before, but one that is very important with respect to aromatic compounds. That group is the nitro group which consists of a nitrogen atom bonded to the ring and bonded to two oxygen atoms, so the nitro group is an -NO2 group that can be bonded to carbon. This is shown in the nitrobenzene.
In many cases when only one group is attached to a benzene ring, you simply name that group and follow that name by the name benzene. This is the case for these two compounds (which are also shown in Example 15 in your workbook). The compound with a nitro group attached to a benzene ring is called nitrobenzene. A benzene ring with a chloro group attached is called chlorobenzene.

nitrobenzene

chlorobenzene

Special Names Many simple aromatic compounds, however, have their own unique name. These are names that are not derived from the word benzene. The only way you would become familiar with them is to memorize them or use them frequently.
Two such compounds are shown here (and also in Example 15 in your workbook). These are toluene and phenol. Toluene is the one that could be called methylbenzene. Phenol could be called hydroxybenzene.

toluene

phenol

Multiple Side Groups When more than one group is attached to the benzene ring, there are two methods that can be used to identify where those groups are attached. One of those methods is a numbering system that is an extension of the IUPAC method and similar to what we have used before with cyclic alkanes. In this

system, one of the groups that is attached to the benzene ring is considered to be attached to the number one carbon atom. The other groups are indicated (as they were before) by a prefix and a number to indicate where they are attached on the benzene ring.

Some examples are given here. Here we have 1,2-dichlorobenzene, 1,3dichlorobenzene, and 1,4-dichlorobenzene. Again, the numbers are chosen in such a way as to give the smallest combination of numbers possible. I should point out that although the #1 carbon atom is usually shown at the top of the structural formula, it does not have to be that way.

1,2-dichlorobenzene

1,3-dichlorobenzene

1,4-dichlorobenzene

There is also another type of notation that is often used. This notation is to use the prefix ortho- to indicate that the two functional groups are on adjacent carbon atoms within the ring. So 1,2-dichlorobenzene can also be called ortho-dichlorobenzene. Sometimes the ortho- prefix is abbreviated just with a small letter o-.

orthodichlorobenzene o-dichlorobenzene metadichlorobenzene m-dichlorobenzene para-dichlorobenzene p-dichlorobenzene

If the functional groups are attached to carbon atoms on the ring which have one carbon between them, then they are referred to as being meta to one another. Thus, 1,3-dichlorobenzene is sometimes called meta-dichlorobenzene. Quite often the meta- is abbreviated by simply using the small letter m-. When the two functional groups are on opposite ends of the ring of carbon atoms, they are referred to as being para to one another, and the third compound here can be referred to as para-dichlorobenzene.

The para- is sometimes abbreviated, using small letter p-.

The ortho, meta, and para prefixes are generally used when only two groups are attached to the benzene ring. This method pretty much falls from use when more than two functional groups are attached. The number method, on the other hand, can be used for any number of functional groups attached to the benzene ring. Some more examples are shown here (and also in Example 17 in your workbook).
The first of these is 4-chlorotoluene. It can also be called para-chlorotoluene. The next compound, 2,4,6-trinitrotoluene, is usually referred to as TNT. Notice that there are three nitro groups attached; and since it is the nitrogen atom that is attached to the ring, the NO2 group in the upper left corner is written in the opposite direction just to emphasize that it is the nitrogen atom that is attached to the ring. The third compound shown here is called pxylene. We will use it in the lab instead of benzene because it is safer to work with. 4-chlorotoluene para-chlorotoluene

2,4,6-trinitrotoluene TNT

p-xylene

Practice You can get some additional practice working with the names of aromatic compounds by figuring out the structural formulas for these compounds for which the formulas are shown below. (These are also shown in Exercise 18 in your workbook.) Please take some time to draw structures for those now.
bromobenzene

o-dibromobenzene 3-bromo-5-chloro-1-nitrobenzene m-ethylisopropylbenzene

Answers
bromobenzene

o-dibromobenzene

3-bromo-5-chloro-1-nitrobenzene

m-ethylisopropylbenzene

Structure
Main article: Aromaticity

Benzene represents a special problem in that, to account for the bond lengths quantitatively, there must either be electron delocalization (MO theory) or a spin coupling of the p-orbitals (VB theory):[33]

The various representations of benzene

X-ray diffraction shows that all six carbon-carbon bonds in benzene are of the same length, at 140 picometres (pm). The CC bond lengths are greater than a double bond, (135 pm), but shorter than a single bond, (147 pm). This intermediate distance is consistent with electron delocalization: the electrons for CC bonding are distributed equally between each of the six carbon atoms. Benzene has 8 hydrogen atoms fewer than the corresponding parent alkane, hexane. The molecule is planar.[34] The MO description involves the formation of three delocalized orbitals spanning all six carbon atoms, while in VB theory the aromatic properties of benzene originate from spin coupling of all six orbitals.[35][36][37][38] It is likely that this stability contributes to the peculiar molecular and chemical properties known as aromaticity. To indicate the delocalized nature of the bonding, benzene is often depicted with a circle inside a hexagonal arrangement of carbon atoms. As is common in organic chemistry, the carbon atoms in the diagram above have been left unlabeled. Realizing each carbon has 2p electrons, each carbon donates an electron into the delocalized ring above and below the benzene ring. It is the side-on overlap of p-orbitals that produces the pi clouds. Derivatives of benzene occur sufficiently often as a component of organic molecules that there is a Unicode symbol in the Miscellaneous Technical block with the code U+232C () to represent it with three double bonds,[39] and U+23E3 () for a delocalized version.[40]

Benzene derivatives
Main articles: Aromatic hydrocarbons and Alkylbenzenes

Many important chemical compounds are derived from benzene by replacing one or more of its hydrogen atoms with another functional group. Examples of simple benzene derivatives are phenol, toluene, and aniline, abbreviated PhOH, PhMe, and PhNH2, respectively. Linking benzene rings gives biphenyl, C6H5C6H5. Further loss of hydrogen gives "fused" aromatic hydrocarbons, such as naphthalene and anthracene. The limit of the fusion process is the hydrogen-free allotrope of carbon, graphite. In heterocycles, carbon atoms in the benzene ring are replaced with other elements. The most important derivatives are the rings containing nitrogen. Replacing one CH with N gives the compound pyridine, C5H5N. Although benzene and pyridine are structurally related, benzene cannot be converted into pyridine. Replacement of a second CH bond with N gives, depending on the location of the second N, pyridazine, pyrimidine, and pyrazine.