Aromatic Compounds

By:

ANITA ESTELA M. MONROY

In the early days of organic chemistry, the word aromatic was used to describe fragrant substances auch as benzaldehyde (from cherries, peaches, and almonds) toluene (from tolu balsam), and benzene (from coal distillate).

Today, we use the word aromatic to refer to the class of compounds that contain benzene-like, six-membered rings with three double bonds.

Many important compounds are aromatic in part, including the steroidal hormone estrone and the analgesic ibuprofen.

Benzene itself causes a depressed white blood cell count (leukemia) on prolonged exposure and should not be used as a laboratory solvent.

Criteria for Aromaticity

1. A compound must have uninterrupted cyclic cloud of p electrons above and below the plane of the molecule

2. The p cloud must contain an odd number of pairs of p electrons

Hckels Rule

For a planar, cyclic compound to be aromatic, its uninterrupted p cloud must contain (4n + 2) p electrons, where n is any whole number

Monocyclic hydrocarbons with alternating single and double bonds are called annulenes

Cyclobutadiene is not aromatic because it has an even number of electron pairs

Cyclooctatetraene is not aromatic because it is nonplanar

Neither cyclopropene nor the cyclopropenyl anion is aromatic

The cyclopropene cation is aromatic

sp3 cycloheptatriene interrupted p cloud not aromatic

sp3 cyclopentadiene 2 pairs of p electrons not aromatic

These compounds are aromatic

To be classified as aromatic, a compound must meet the following criteria: (Criteria for Aromaticity)
It must have an uninterrupted cyclic cloud of pi electrons (called a pi cloud) above and below the plane of the molecule. That is: > For the cloud to be cyclic, the molecule must be cyclic. > For the pi cloud to be uninterrupted, every atom in the ring must be a p orbital. > For the pi cloud to be formed, each p orbital must overlap with the p orbitals on either side of it. Therefore, the molecule must be planar. The pi cloud must contain an odd number of pairs of pi electron.

Aromaticity and the 4n + 2 Rule

Huckels rule, based on calculations a planar cyclic molecule with alternating double and single bonds has aromatic stability if it has 4n+ 2 p electrons (n is 0,1,2,3,4) For n=1: 4n+2 = 6; benzene is stable and the electrons are delocalized

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Compounds With 4n p Electrons Are Not Aromatic (May be Antiaromatic)

Planar, cyclic molecules with 4 n p electrons are much less stable than expected (anti-aromatic) They will distort out of plane and behave like ordinary alkenes 4- and 8-electron compounds are not delocalized (single and double bonds) Cyclobutadiene is so unstable that it dimerizes at low temperature Cyclooctatetraene has four double bonds, reacting with Br2, KMnO4, and HCl as if it were four alkenes

cyclobutadiene

cyclooctatetraene

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A compound is antiaromatic if it is a planar, cyclic compound with an uninterrupted ring of p cloud, but it contains even number of pairs of p electrons

Aromatic Ions
The 4n + 2 rule applies to ions as well as neutral species Both the cyclopentadienyl anion and the cycloheptatrienyl cation are aromatic The key feature of both is that they contain 6 p electrons in a ring of continuous p orbitals

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Aromaticity of the Cyclopentadienyl Anion

1,3-Cyclopentadiene contains conjugated double bonds joined by a CH2 that blocks delocalization Removal of H+ at the CH2 produces a cyclic 6-electron system, which is stable Removal of H- or H generate nonaromatic 4 and 5 electron systems Relatively acidic (pKa = 16) because the anion is stable

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Cycloheptatriene
Cycloheptatriene has 3 conjugated double bonds joined by a CH2 Removal of H- leaves the cation The cation has 6 electrons and is aromatic

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Aromatic Heterocycles: Pyridine and Pyrrole

Heterocyclic compounds contain elements other than carbon in a ring, such as N,S,O,P Aromatic compounds can have elements other than carbon in the ring There are many heterocyclic aromatic compounds and many are very common Cyclic compounds that contain only carbon are called carbocycles (not homocycles) Nomenclature is specialized

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Aromatic Heterocyclic Compounds

A heterocyclic compound is a cyclic compound in which one or more of the ring atoms is an atom other than carbon

Examples of Heterocyclic Aromatic Compounds

 Aromatic Heterocyclic Compounds a cyclic compound in which one (or more) of the ring atoms is an atom other than carbon A heteroatom is a ring atoms that is not carbon (usually N, O, and S).
N

N
..

pyridine

Pyridine
A six-membered heterocycle with a nitrogen atom in its ring p electron structure resembles benzene (6 electrons) The nitrogen lone pair electrons are not part of the aromatic system (perpendicular orbital) Pyridine is a relatively weak base compared to normal amines but protonation does not affect aromaticity

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Pyrrole
A five-membered heterocycle with one nitrogen p electron system similar to that of cyclopentadienyl anion Four sp2-hybridized carbons with 4 p orbitals perpendicular to the ring and 4 p electrons Nitrogen atom is sp2-hybridized, and lone pair of electrons occupies a p orbital (6 p electrons) Since lone pair electrons are in the aromatic ring, protonation destroys aromaticity, making pyrrole a very weak base

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Why 4n +2?
When electrons fill the various molecular orbitals, it takes two electrons (one pair) to fill the lowest-lying orbital and four electrons (two pairs) to fill each of n succeeding energy level This is a total of 4n + 2

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Polycyclic Aromatic Compounds: Naphthalene

Aromatic compounds can have rings that share a set of carbon atoms (fused rings) Compounds from fused benzene or aromatic heterocycle rings are themselves aromatic

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Naphthalene Orbitals
Three resonance forms and delocalized electrons

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Benzene, the parent substance of the aromatic hydrocarbons was first isolated by Michael Faraday in 1825, its correct molecular formula, C6H6 was established a few years later.

In 1865, August Kekule proposed that the carbon atoms in a benzene molecule are arranged in a six-membered ring with one hydrogen atom bonded to each carbon atom and with three carbon to carbon double bonds.

These three C to C bonds are in rapid oscillation within the molecule, hence the resonance forms.
Benzene and its related substances are highly unsaturated yet does not react like a typical alkene.

It does not decolorize bromine solutions rapidly, nor destroy the purple color of the permanganate ions (Baeyers test).

Benzene, instead behaves chemically like a typical alkane. Its reactions are usually substitution type, wherein hydrogen atom is replaced by some other group, like Cl from Cl2.
The orbital hybridization of the carbon atoms in benzene is sp2 . The electrons composing the clouds of the pi bonds are not attached to a particular carbon atoms but are delocalized and associated with the entire molecule. This electronic structure imparts unusual stability to benzene and is responsible for the many characteristic properties of aromatic compounds. Due to this stability benzene does not readily undergo addition or elimination reaction but substitution reactions. Naming Aromatic Compounds: - Substituted benzenes are the most common benzene derivatives because substitution is the most common reaction type for benzene. - The general formula for monosubstituted benzene is C6H5G, where G is the substituent.

Monosubstituted benzenes are named by adding the name of the substituent group as a prefix to the word benzene. The name is written as one word. The position of the substituent is not important, because all the positions are equivalent.
O N+ O-

Cl

Br

nitrobenzene

ethylbenzene

chlorobenzene

bromobenzene

Certain monosubstituted benzenes have special names:

OH

toluene

phenol

styrene

(Methylbenzene)

(Hydroxybenzene)

(Vinylbenzene)

HO

OH

benzoic acid (benzen carboxylic acid) O

NH2

benzaldehyde
(Benzene carboxaldehyde)

aniline
(Aminobenzene)

The Phenyl Group

When a benzene ring is a substituent, the term phenyl is used (for C6H5 )
You may also see Ph or f in place of C6H5

Benzyl refers to C6H5CH2

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These can be used as parent names for further substituted compounds.

The C6H5 group is known as the phenyl group. Phenyl is used to name compounds that cannot easily be named as benzene derivatives. For example:

Cl

3-chloro-2-phenylpentane

diphenylmethane

Disubstituted Benzenes: When two substituent groups replace two hydrogen atoms in a benzene molecule, three different isomeric compounds are possible.

The prefixes ortho- , meta-, para-, (abbreviated o-, m-, p-) are used to name disubstituted benzenes. Ortho (1,2 position), meta (1,3 position), para (1,4 position)
Cl
-

O N+ O

Cl

o-dichlorobenzene

m-ethylnitrobenzene

p-xylene

Dimethylbenzene have a special name xylene

Disubstituted Benzenes
Relative positions on a benzene ring
ortho- (o) on adjacent carbons (1,2) meta- (m) separated by one carbon (1,3) para- (p) separated by two carbons (1,4)

Describes reaction patterns (occurs at the para position)

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When one of the substituents corresponds to a monosubstituted benzene, that has a special name, the disubstituted compound is named as a derivative of that parent compound. Ex.:
OH O N+ O-

O
Br NH2

N+ O-

o-nitrophenol

p-bromoaniline

m-nitrotoluene

The numbering system as described under polysubstituted benzenes is also used to name disubstituted benzenes.. When more than two substituents are present on a ring, the carbon atoms are numbered starting at one of the substituted groups. Numbering may either be clockwise or counterclockwise, but must be done in the direction that gives the lowest possible numbers to the substituent groups.

Naming Benzenes With More Than Two Substituents

Choose numbers to get lowest possible values List substituents alphabetically with hyphenated numbers Common names, such as toluene can serve as root name (as in TNT)

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When the compound is named as a derivative of one of the special parent compounds, the substituent of the parent compound is considered to be on carbon 1 of the ring. Br O

N+ O N+ O-

N+ O N+ O-

Br

Br

1,2,4-tribromobenzene
Cl

N+ O

N+ O-

1,3,5-trinitrobenzene

2,4,6-trinitrotoluene

HO

Br

5-bromo-2-chlorophenol

Polycyclic Aromatic Compounds

> There a many other aromatic ring systems besides benzene. There structures consists of two or more rings in which two carbon atoms are common to two rings.

> These compounds are known as polycyclic or fused aromatic ring systems. Three of the most common hydrocarbons in this category are: naphthalene, anthracene, and phenanthrene. One hydrogen is attached to each carbon atom, except at the carbons common to the two rings.

naphthalene

phenanthrene

anthracene

Sources and Physical Properties of Aromatic HC:

When coal is heated to high temperatures (450 -1,200 C) in the absence of air to produce coke (C) , coal gas and a complex mixture of condensable substances called coal tar are driven off. Coal Coke + Coal gas + Coal tar

The aromatic HC such as benzene, toluene, xylene, naphthalene, and anthracene were first obtained in significant quantities from coal tar. Since coal tar itself is a by-product of the manufacture of coke, the total amount of aromatics that can be obtained from this source is limited. Aromatic HCs are used in the production of a vast number of materials such as drugs, dyes, detergents, explosives, insecticides, plastics, and synthetic rubber, hence the demand. Processes were devised to make aromatic HCs from the inexpensive alkanes found in petroleum.

Sources of Aromatic Hydrocarbons

From high temperature distillation of coal tar Heating petroleum at high temperature and pressure over a catalyst

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Currently, about 1/3 of our benzene supply and the greater portion of our toluene and xylene supplies are obtained from petroleum. Aromatic HCs are essentially nonpolar substances, insoluble in water but soluble in many organic solvents

They are liquids or solids and usually have densities lower than water.

They burn readily, usually smoky yellow flames as a result of incomplete carbon combustion.

Some are blended with other HCs to make good motor fuels with excellent antiknock properties.

Chemical Properties of Aromatic HCs The most characteristic reactions of aromatic HCs involve the substitution of some group for hydrogen on one of the ring carbons. (Note that substitution reactions do not change the number of atoms bonded to each carbon. H O X C R Halogenation NO2 SO3H Alkylation Nitration Sulfonation Acylation R

Chemical Properties of Aromatic HCs

1. Halogenation (Cl or Br) . When benzene reacts with Cl or Br in the presence of a catalyst such as iron(III)chloride or iron(II)bromide, a Cl or a Br atom replaces an H atom to form the products.

X2 FeX3
benzene

X + HX

Br + Br2 FeBr3 + HBr

benzene

2. Nitration. When benzene reacts with a mixture of concentrated nitric acid and concentrated sulfuric acid at about 50oC, nitrobenzene is formed.
H2SO4 NO2 + H2 O

+ HO NO2
benzene

3. Sulfonation. Aromatic rings are sulfonated by reaction with fuming sulfuric acid, a mixture of SO3 and H2SO4. The reactive electrophile is HSO3 +, and substitution occurs just like that of halogenation. Aromatic sulfonation is a key step in the synthesis of compounds as the sulfa drug family of antibiotics. SO3 + H2SO3 + SO3 H2SO4 catalyst
benzene

SO3H +

HSO4 SO3H

Benzenesulfonic acid

4. Alkylation (Friedel-Crafts reaction). There are many variations of the friedel-Crafts reaction. In this type the alkyl group from an alkyl halide (RX) in the presence of AlCl3 catalyst, substitutes for an H atom on the benzene ring.

+ CH3CH2Cl
benzene

AlCl3

CH2CH3
+ HCl

From about 1860 onward, especially in Germany, a great variety of useful substances such as dyes, explosives, and drugs were synthesized from aromatic HCs by this type of reaction. Aromatic substitution reactions usually proceed by a mechanism called electrophilic substitution which follows the following steps:

Step 1. An electrophile (electron-seeking group) is formed.

FeCl3 + Cl2 FeCl4 + Cl

Chloronium ion(electrophile)

Step 2. The electrophile is attached to the benzene ring, forming a positivelycharged carbocation intermediate
H Cl

+ Cl +
benzene

A carbocation

Step 3. A hydrogen ion is lost from the carbocation to form the product. H Cl Cl

+ FeCl4

+ FeCl3 + HCl
benzene chlorobenzene

Note: The catalyst FeCl3 is regenerated in step 3. Nitration and alkylation also proceed by an electrophilic mechanism.

4. Freidel-Crafts acylation reaction. When an aromatic compound is treated with a carboxylic acid chloride, RCOCl, in the presence of AlCl3, an acyl group, - COR, is introduced to the ring.Ex.:

+
O

Cl

AlCl3 80oC
O

benzene

acetyl chloride

acetophenone

(95%)

Substituent Effects in Electrophilic Aromatic Substitution > Only one product can be formed when an electrophilic substitution occurs on benzene. But what could happen if we carry out an electrophilic substitution reaction on a ring that has already a substituent?

> Substituents already present on an aromatic ring has two effects:

1. It affects the reactivity of the aromatic ring. It may activate the ring for further electrophilic substitution, and some may deactivate it. * An OH group activates the ring, making phenol (hydroxybenzene) 1,000 times more reactive than benzene toward nitration. * An NO2 group deactivates the ring, however making nitrobenzene 20 million times less reactive than benzene.
O N+ O-

Cl

OH

nitrobenzene

chlorobenzene

benzene

phenol

Relative Rate of nitration: 6 x 10 -8 0.033 1 1,000

Reactivity

2. Substituent affect the orientation of the reaction.

The three possible disubstituted products; ortho-, meta - , paraare usually not formed in equal amounts. An - OH group directs further substitution toward the ortho and para positions. -CN group directs further substitution toward the meta position.
OH

O
OH

HNO3 H2SO4, 25oC

N
+

HO

N+ O-

phenol
o-nitrophenol

p-nitrophenol

(50%)

(50%)

O N+ O-

17%

o-nitrobenzonitrile
N

HNO3
benzonitrile

H2SO4,25oC
-

O N+ N O

81%

m-nitrobenzonitrile
O N N+ O-

2%

p-nitrobenzonitrile

Substituents can be classified into three groups: * ortho- and para- directing activators * ortho- and para-directing deactivators * meta- directing deactivators. * The halogens are unique in being ortho- and para- directing deactivators.

No meta- directing activators are known All meta-directing groups are deactivators, and most ortho- and paradirecting groups are activating.

Side-chain Oxidation: Carbon chains attached to an aromatic ring are fairly easy to oxidize. Reagents most commonly used are KMnO4 or K2Cr2O7 + H2SO4.

No matter how long the side chain is, the carbon atom attached to the ring is oxidized to a carboxylic acid group, -COOH.
O

KMnO4 / H2O
toluene
benzoic acid
O

OH

K2Cr2O7 / H2SO4
ethylbenzene

+ CO2
OH

benzoic acid
O

K2Cr2O7 / H2SO4
propylbenzene

+ CH3COOH
OH

benzoic acid

Choose the letter of the best answer:

1. The formula CH3CH2CH2 + is a A. Primary carbocation B. Secondary carbocation 2. Which of the following is aniline? A.
O
O

C. Tertiary carbocation D. Quaternary carbocation

C.

N+ O-

B.

NH2

D.

3. Which of the following compounds is 2-chloro-4-nitrotoluene?

Cl Cl O-

A.

N+ O

C.

HO N+ O

O-

OH

O-

B.
-

N+ O

Cl

D.

N+ O Cl

4. Which of the following is m-xylene?

O

A.
Cl Cl

C.
HO

B.
HO OH

D.

5. Give the IUPAC name of the compounds in 5.26 p.172. 6. Draw the structures, given the name on p.172 5.27 7. 5.33 p.173