Aromatic compounds

Introduction
Organic compounds Aliphatic cpds Aromatic cpds

Aromatic compound an organic compound that contains a benzene ring in its molecule. Benzene is an example of aromatic ring with the molecular formula, C6H6.

Aromatic compounds
Sometimes called arenes.

Benzene
Colourless liquid with a characteristic smell Highly flammable and burns with a smoky yellow flame Insoluble in water but soluble in all organic solvents Molecular formula: C6H6 The presence of three carbon-carbon double bonds per molecule

Types of aromatic compounds

 There are two classifications of aromatic compounds. Nuclear Substituted Compounds When the functional group or any substituent directly attached to the benzene ring. Named as the derivatives of benzene under the IUPAC system. However, the common names of many such compounds are retained by IUPAC.

Sidechain Substituted Compounds the functional group is present in the sidechain of the ring. Named as the phenyl derivatives of the corresponding aliphatic compounds.

Naming Benzene Derivatives Only one kind of monosubstituted derivatives are possible in benzene rings as all six hydrogen atoms are equivalent. For example, there is only one toluene. It does not matter where the methyl group is attached because all the following arrangements are equivalent. When two same or different monovalent substituents, are present on a benzene ring, the following three arrangements are possible.

For the same substituent (A)

ortho (or, 1,2-) meta-(or, 1,3-)

para- (or, 1,4)

 For different substituents (A and B)

ortho (or, 1,2-)

meta-(or, 1,3-)

para- (or, 1,4)

These arrangements are named as follows: The compound containing the two groups on the adjacent sites is called 'ortho'; it is denoted as 'o-'. In the IUPAC system, the ortho position is designated as 1,2-. The compound containing the two groups on alternate sites is called 'meta': it is denoted as 'm-'. In the IUPAC system,the meta position is designated as 1,3-.

 The compound containing the two groups diagonally opposite to each other is called 'para': denoted as 'p-'. In the IUPAC system, the para position is designated as 1,4-. For example, the three xylenes are named as,

o-xylene (1,2-dimethylbenzene)

m-xylene (1,3-dimethylbenzene)

p- xylene (1,3-dimethylbenzene)

 In the case of trisubstituted derivatives, the nature of the substituted groups determine the number of arrangements. When the three substituent groups are identical (say, A), three arrangements are possible. These are termed as follows.

vicinal (vic-)

unsymmetrical (unsym-) symmetrical (sym-)

 For a trisubstituted product, if the two substituents are identical and the third different, then six products are possible. When all the three groups are different, ten products are possible. Since, naming each individual compound is not possible, it was found convenient to indicate the position of any substituent by the numeral indicating the serial number of the carbon atom in the ring, to which that substituent is attached.

Numbering the Carbon Atoms in the Ring The numbering of carbon atoms in the ring (or nucleus) is done as follows. When there is only one substituent on the ring, there is only one compound possible. Thus, numbering of the carbon atoms of the nucleus does not arises.

 If there are two or more substituents, then numbering is in the alphabetical order of the substituents on the carbon atoms. The prefixes such as 'di', 'tri', 'cyclo', 'iso', etc., are ignored while arranging the substituents alphabetically. When two or more functional groups are present, then the principal functional group is assigned the number 1. The order of priority of the functional groups is the same as done for aliphatic polyfunctional compounds.

 For the sake of convenience, the ring is oriented in such a way that position 1 is at the top and numbering is done in a clockwise or anticlockwise manner whichever gives lower numbers to the other substituents.

 This is illustrated through the following example. The IUPAC names are written in bold letters.

(o-xylene) 1,2-dimethylbenzene

(m-xylene) 1,3-dimethylbenzene

(p-xylene) 1,4-dimethylbenzene

Names of some typical aromatic compounds are given below: Aromatic hydrocarbons (arenes)

toluene Methylbenzene

o-xylene 1,2-dimethylbenzene

m-xylene 1,3-dimethylbenzene

p-xylene 1,4-dimethylbenzene

1,3,5-trimethylbenzene

2-phenylpropane (cumene) phenylethene (styrene)

Anthracene

Phenonthrene

Halogen derivatives

2-chlorotoulene

1,2-dichlorobenzene

phenyl chloromethane

Hydroxy derivatives: Phenols and aromatic alcohols

2-methyl phenol

phenylmethanol

1,4-dihydroxy benzene

2,4,6-trinitrophenol

Aldehydes and Ketones Nuclear substituted

Benzaldehyde

Methyl phenyl ketone

Diphenyl ketone

Carboxylic acids Nuclear substituted

benzoic acid

2-methylbenzoic acid

2-hydroxybenzoic acid 1,4-benzenedicarboxylic acid

Acid derivatives

Benzoyl chloride

Benzamide

Phenyl benzoate

Benzoic anhydride

Ethyl-4-bromobenzoate

Alkoxy derivatives

Methoxy benzene

4-nitrobenzene

1-methoxy-phenoxybenzene

Amines

Aminobenzene

2-Amino toluene

Benzyl amine

Nitro derivatives

nitrobenzene

1,3-dinitrobenzene

2,4,6-trinitrotoluene

Nitriles and Carbylamines

Benzonitrile

Phenylcarbylamine

Sulphonic acids

benzenesulphonic acid

benzene-1,3-disulphonic acid

Naming Aromatic Compounds Aromatic compounds are those carbocyclic compounds that contain at least one benzene ring. The ring of six carbons in benzene or any of its derivatives is termed benzene ring or nucleus. A benzene ring may be represented in any of the following ways.

 Any aliphatic group attached to the benzene ring is termed as the sidechain as shown alongside. In this structure R may be CH3, CH2Cl, CH2OH or CH2NH2. However, the functional groups such as NO2, OH, NH2, etc., and any other non-carbon substituent, linked directly to the nucleus are called as the sidechain.

 Aromatic compounds may be classified as follows. Monocyclic Aromatic Compounds Monocyclic aromatic compounds are those that contain only one six-membered benzene ring. The following compounds are some examples of monocyclic aromatic compounds.

Multicylic Aromatic Compounds Aromatic compounds containing two or more benzene rings, condensed with each other, are known as multicyclic aromatic compounds or polynuclear aromatic compounds. Some typical examples of polynuclear aromatic compounds are,

Aryl Group Aromatic hydrocarbons are called arenes. When one or more hydrogens are removed from the aromatic hydrocarbons, the residues left behind are termed as aryl groups (similar to alkyl groups in the case of aliphatic hydrocarbons). The aryl groups are represented by Ar.

 Some typical aryl groups are:

Aromaticity: Importance Of Aromatic Compounds Aromatic compounds are important in industry. Key aromatic hydrocarbons of commercial interest are benzene, toluene, ortho-xylene and para-xylene. About 35 million tonnes are produced worldwide every year. They are extracted from complex mixtures obtained by the refining of oil or by distillation of coal tar, and are used to produce a range of important chemicals and polymers, including styrene, phenol, aniline, polyester and nylon.

 Other aromatic compounds play key roles in the biochemistry of all living things. Three aromatic amino acids phenylalanine, tryptophan, and tyrosine, each serve as one of the 20 basic building blocks of proteins.

 Further, all 5 nucleotides adenine, thymine, cytosine, guanine, and uracil that make up the sequence of the genetic code in DNA and RNA are aromatic purines or pyrimidines. As well as that, the molecule haem contains an aromatic system with 22 electrons. Chlorophyll also has a similar aromatic system.

Reactions of Aromatic Compounds

 Unlike alkenes, which undergo addition reactions, aromatic compounds usually undergo substitution reactions. A group Y substitutes for one of the hydrogen atoms on the aromatic ring without changing the ring itself.

A substitution reaction

 The most common reaction of aromatic compounds is the electrophilic aromatic substitution. An electrophile (E+ ) reacts with an aromatic ring No addition reactions of alkenes: no decolorisation of bromine or potassium manganate(VII) solution no reaction with HCl, HBr or concentrated H2SO4

Substitution reaction
1. Halogenation 2. Nitration 3. Friedel-Crafts reaction i. Alkylation ii. Acylation 4. Sulphonation

Halogenation
Substitution of a bromine or chlorine (Br/Cl) for a ring hydrogen occurs when benzene reacts with Br2 or Cl2. a hydrogen atom a halogen atom Catalyst: FeBr3 or FeCl3 Bromination

Benzene

Bromobenzene

Chlorination

Benzene

Chlorobenzene

Nitration
Substitution of a nitro group ( NO2) for a ring hydrogen occurs when benzene reacts with nitric acid. a hydrogen atom a nitro group, NO2 Catalyst: sulphuric acid, H2SO4

Benzene

Nitrobenzene

Friedel-Crafts reaction
i. Alkylation: the attachment of an alkyl group to the benzene ring. a hydrogen atom an alkyl group from haloalkane to form an alkylbenzene Benzene ring can be alkylated by reaction with an alkyl chloride. Catalyst: aluminium chloride

For example:
The Friedel- Crafts alkylation of benzene with methyl chloride

Methyl chloride

Benzene

Methylbenzene

ii. Acylation: a hydrogen atom an acyl group from an acyl halide to form an aromatic ketone An acyl group, -COR is introduced onto the ring when an aromatic compound reacts with a carboxylic acid chloride, RCOCl. Catalyst: AlCl3

For example
Reaction of benzene with acetyl chloride yields the ketone, aceptophenone.

AlCl3

Benzene

Acetyl chloride

Aceptophenone

Sulphonation
Aromatic rings can be sulphonated by reaction with fuming sulfuric acid, a mixture of H2SO4 & SO3. a hydrogen atom an SO3H group the only reversible aromatic substitution. Sulphonation is favored in strong acid; desulphonation is favored in hot, dilute aqueous acid.

For example

Benzene

H2SO4 + SO3

Benzenesulfonic acid

Properties of aromatic compounds

Physical characteristic
Benzene is a colourless liquid with a characteristic smell. Both the liquid and the vapour of benzene are highly poisonous.

Density
Aromatic compounds are more dense than other hydrocarbons, but less dense than water It has a density of 0.88g cm-3.

Boiling points
In benzene, the only attractions between neighbouring molecules are van der Waals dispersion forces. There is no permanent dipole on the molecule. Benzene boils at 80C - rather higher than other hydrocarbons of similar molecular size (pentane and hexane, for example).

 This is presumably due to the ease with which temporary dipoles can be set up involving the delocalised electrons It is highly flammable and burns with a smoky yellow flame.

Melting points
Melting point of benzene is higher than methylbenzene. Benzene melts at 5.5C while methylbenzene melts at -95C. Molecules must pack efficiently in the solid if they are to make best use of their intermolecular forces. Benzene is a tidy, symmetrical molecule and packs very efficiently.

Solubility
The arenes are insoluble in water. Benzene is quite large compared with a water molecule. In order for benzene to dissolve it would have to break lots of existing hydrogen bonds between water molecules. Energy would also needed to break the quite strong van der Waals dispersion forces between benzene molecules. Both of these cost energy.

 Benzene is soluble in all organic solvents. It is a very good solvent for fats, organic compounds with low relative molecular mass and inorganic substances such as iodine and sulphur.

Methylbenzene
Methylbenzene is a colourless liquid which smells like benzene.

Boiling Point
Methylbenzene boils at 111C. It is a bigger molecule and so the van der Waals dispersion forces will be bigger. Methylbenzene also has a small permanent dipole, so there will be dipole-dipole attractions as well as dispersion forces. The dipole is due to the CH3 group's tendency to "push" electrons away from itself. This also affects the reactivity of methylbenzene.

Melting Point
Methybenzenes melting point (-95C) is lower than that of benzene (5C) even though its relative molecular mass is larger than benzene. This because the planar molecules of benzene can pack close together and the intermolecular forces of attraction are therefore stronger.

 In contrast, the methyl group in methylbenzene prevents such close packing. Thus, the melting point of methylbenzene is lower than that of benzene.

If the molecules aren't as closely packed, the intermolecular forces don't work as well and so the melting point falls.

Uses of aromatic compounds

 Nitration - Nitration of aromatic rings is a key step in the synthesis of explosives such as TNT (trinitrotoluene) & many important pharmaceutical agents. - Nitrobenzene is a starting material for preparing many of the brightly coloured dyes used in clothing.

 Halogenation - chlorination of an aromatic ring is a step used in the synthesis of numerous pharmaceutical agents, such as the antianxiety agent diazepam, marketed as Valium.

 Sulphonation - aromatic sulphonic acids are valuable intermediates in the preparation of dyes and pharmaceuticals. Eg: the sulfa drugs such as sulfanilamide were among the first useful antibiotics. These drugs are prepared commercially by a process that involves aromatic sulphonation as the key step.