Benzene a remarkable compound Chapter 14 Aromatic Compounds

t Discovered by Faraday 1825 t Formula C6H 6 t Highly unsaturated, but remarkably stable t Whole new class of benzene derivatives called aromatic compounds

Nomenclature of Benzene Derivatives

Some proposed structures for C6H6

Benzene is the parent name for some monosubstituted benzenes

For other monosubstituted benzenes, the presence of the substituent results in a new parent name

When two substituents are present their position may be indicated by the prefixes ortho, meta, and para (o , m and p ) or by the corresponding numerical positions

Dimethyl substituted benzenes are called xylenes

ortho = at right angles para = across (meta = above, behind, beyond = middle

Numbers must be used when more than two substituents

1. 2. 3.

C 6H5- group is called phenyl when it is a substituent

Phenyl is abbreviated Ph or A hydrocarbon with a saturated chain and a benzene ring is named by choosing the larger structural unit as the parent t If the chain is unsaturated then it must be the parent and the benzene is then a phenyl substituent
t t

Assign the lowest possible set of numbers Substituents are in alphabetical order If one of the substituents defines the parent name, it is designated as position 1 (and not stated)

The phenylmethyl group is called a benzyl (abbreviated Bz )

Reactions of Benzene
t Even though benzene is highly unsaturated, it does not

Reactions of Benzene
t Benzene can be induced to react with bromine if a Lewis

undergo any of the regular reactions of alkenes

acid catalyst is present

t The reaction is a substitution and not an addition!

Benzene produces only one monobrominatedcompound All 6 carbon-hydrogen bonds are equivalent in benzene

tThe Kekule Structure for Benzene

t

What is the Stability of Benzene?

Kekule was the first to formulate a reasonable representation of benzene

The Kekule structure suggests alternating double and single bonds

l Oone would expect there to be two different 1,2-dibromobenzenes l But there is only one l Kekule suggested an equilibrium between these compounds

Doesnt explain stability!

The Resonance Explanation of Benzene

t Benzene is particularly stable because it has two equivalent

Molecular Orbital Picture of Benzene

t Each carbon in benzene is sp 2 hybridized with a p orbital l The p orbitals overlap around the ring to form a bonding

resonance structures
t C-C bond length is 1.39 l C-C single bond between sp 2 carbons (1.47) l C-C double bond (1.33 )

molecular orbital with electron density above and below the plane of the ring

Molecular Orbital Theory gives superior explanation

Simple resonance explanation is incomplete

Recap of MO Theory
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t MO theory describes bonds as the combination of atomic

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orbitals that form a new set of orbitals called molecular orbitals (MOs). t A molecular orbital occupies a region of space in a molecule where electrons are likely to be found. t We will look only at qualitative version of a mathematically rigorous treatment t For systems involving p bonds, we can focus only on p orbitals

Cyclooctatetraene rapidly decolorizes bromine

The MO view of a double bond

The combination of two p orbitals can be constructivethat is, with like phases interactingor destructive, that is, with opposite phases interacting.

Molecular Orbital Picture of Benzene

Six p orbitals must generate six molecular orbitals for benzene

bond

* antibond

When two p orbitals of similar phase overlap side-b y - side, a bonding molecular orbital results. When two p orbitals of opposite phase overlap side -b y -side, a * antibonding orbital results.

3 bonding MOs, 3 anti-bonding MOs

Net bonding interactions for each benzene orbital

Huckels Rule: The 4n+2 Rule

t Planar monocyclic rings with a continuous system of p
l Aromatic means substantial resonance stabilization

0 6 = -6

orbitals and 4n + 2 electrons are aromatic (n = 0, 1, 2, 3 etc)

l Benzene is aromatic:
planar Cyclic orbital at every carbon 6 electrons (n=1)

0 2 = -2

2 4 = -2

42=2

20=2 t Benzene has 3 bonding and 3 antibonding orbitals

l All the bonding orbitals are full and there are no electrons in

60=6

antibonding orbitals; benzene has a closed shell of delocalized electrons and is very stable

Benzene Molecular Orbitals and the 4n+2 Rule

t

General picture of cyclic p system MO s

The polygon-and-circle method depicts the relative energies of orbitals of a system with a cyclic continuous array of p orbitals
1. A polygon corresponding to the ring is inscribed in a circle

All bonding orbitals are full Antibonding orbitals are empty Closed shell of delocalized electrons = very stable

with one point of the polygon pointing directly down

2. A horizontal line is drawn where vertices of the polygon

touch the circle - each line corresponds to the energy level of the MOs at those atoms 3. A dashed horizontal line half way up the circle indicates the separation of bonding and antibonding orbitals

Sample polygons illustrate Huckels Rule

Benzene

Cyclooctatetraene: two nonbonding orbitals each with one electron

cyclooctatetraene adopts nonplanar conformation with localized p bonds to avoid this instability

Annulenes and the 4n+2 Rule

t Annulenes = monocyclic compounds with continuous p bonds l Named using a number in brackets to indicate ring size l Example: cyclooctatetraene is [8]annulene l An annulene is aromatic if it has 4n+2 electrons and a

Why the 4n +2 rule works

For the compound to be aromatic, these MOs must be completely filled with electrons, so the magic numbers for aromaticity fit Hckels 4n + 2 rule.

planar carbon skeleton

t The [14]and [18]annulenes are aromatic (4n+2, where n= 3,4) l The [16] annulene is not aromatic

NMR Evidence for Aromaticity

The [10]annulenes could be aromatic but none of them can be plan ar
l 4 is not planar because of steric interaction of the indicated

hydrogens l 5 and 6 are not be planar because of large angle strain in the flat molecules

When benzene is placed in a strong magnetic field a -electron ring current is induced which reinforces the applied magnetic field at the location of the protons
l Protons of benzene are highly deshielded (a singlet at 7.27)

t Cyclobutadiene is a [4]annulene and is not aromatic

Protons on the periphery of aromatic compounds are deshielded

l Deshielding of these protons is physical evidence for aromaticity

Ring current of aromatic systems also produces regions of shielding l In large annulenes, internal protons are highly shielded l In [18]annulene the protons along the outside of the ring appear at 9.3 whereas those on the inside of the ring appear at -3.0 (above TMS = very highly shielded)

A strained [10}-annulene

Vinyl protons 6.8-7.5 d CH2 group at 0.5 d

Aromatic Ions
Cyclopentadiene is extraordinarily acidic (pKa = 16) !

Aromatic Ions
t Cycloheptatriene is not aromatic because its electrons are not

delocalized around the ring (CH2 group is an insulator) l Lose of hydride produces the aromatic cycloheptatrienyl cation (tropylium cation)
Cyclopentadienyl anion has 6 electrons in a cyclic, continuous electron system, and hence follows the 4n + 2 rule for aromaticity

Why Huckels Rule applies to ions

Aromatic, Antiaromatic, and Nonaromatic Compounds

t A comparison of annulenes with their acyclic counterparts

provides a measure of the stability conferred by aromaticity l If the ring has lower -electron energy than the open chain, then it is aromatic l If the ring has the same -electron energy as the open chain, then it is nonaromatic l If the ring has higher -electron energy than the open chain, then it is antiaromatic

Other Aromatic Compounds

t

Benzenoid Polycyclic Aromatic Compounds

Two or more benzene rings fused together

Naphthalene can be represented by three resonance structures l The 10 electrons of napthalene are delocalized and that it has substantial resonance energy

Pyrene has 16 electrons, a non-Huckel number, yet is known to be aromatic

t

Graphite = the ultimate aromatic

By ignoring the central double bond, the periphery of pyrene has 14 electrons, a Huckel number, and on this basis it resembles the aromatic [14]annulene

NMR: Methyl singlets at -4.25 d

New Forms of Carbon 1985, 1991

Buckminsterfullerene (C60) is a third elemental form of carbon. Buckminsterfullerene is completely conjugated, but it is not aromatic since it is not planar. It undergoes addition reactions with electrophiles in much the same way as ordinary alkenes. Carbon nanotubes are rolled graphite (1990s)

Azulene the blue hydrocarbon

t Stable 10 pi electron system t Dark blue crystals t Has a dipole moment of 1.0 Debye (v s 1.8 for chloromethane)

Ferrocene a remarkable aromatic compound

Heterocyclic Aromatic Compounds

t Heterocyclic compounds have an element other than

carbon as a member of the ring l Common names dominate l Numbering always starts at the heteroatom l If there is a cyclic p system, Huckels rule applies

Fe

t Ferrocene discovered in 1951 t Orange crystals that sublime rather than melt t Air stable and stable to > 500o C t Sandwich structure with all carbons equivalent

Pyridine
t t

Pyrrole
t

An sp2 hybridized nitrogen in place of a C -H in benzene

The p orbital on nitrogen is part of the aromatic system of the ring t The nitrogen lone pair is in an sp2 orbital orthogonal to the p orbitals of the ring; these electrons are not part of the aromatic system t The lone pair on nitrogen is available to react with protons and so pyridine is basic

The nitrogen in pyrrole is sp2 hybridized and the lone pair resides in the p orbital l This p orbital with its two electrons participates in the aromatic system l The lone pair of pyrrole is part of the aromatic system and not available for protonation; pyrrole is therefore not basic

N
N

..

4n+2 = 6 pelectrons

4n+2 = 6 p electrons

t In furan and thiophene one electron pair on the heteroatom is

also in a p orbital which is part of the aromatic system

t The remaining non-bonded pair does not participate in the p

Several amino acids have aromatic rings

system

Purine rings

Spectroscopy of Aromatic Compounds t 1H NMR Spectra

l Protons of benzene derivatives are highly deshielded

and appear in the region 6.0 to 9.5

A ring current is induced in the benzene ring that reinforces the applied magnetic field in the region of the protons in benzene

adenine

13C

NMR Spectra

l Aromatic carbons generally appear in the 100-170

region
DEPT spectra will show these carbons to have one or no protons attached

 Example : the spectrum of 4- N,N-diethylaminobenzaldehyde

H

The assignment of carbons (d) and (c) is possible because carbon s (d) should have higher electron density than carbons (c), based on resonanc e structures

Given a molecular formula or mass spectrometric data, 1 3C NMR can be used to recognize compounds with high symmetry
H

The spectrum below corresponds to the last isomer which can have only two peaks

lInfrared Spectra of Substituted Benzenes

t

Benzene derivatives show several characteristic frequencies l C-H Stretching occurs near 3030 cm-1 l Stretching motions of the ring give bands at 1450-1600 cm-1 and two bands near 1500 and 1600 cm-1 t Monosubstituted benzenes show two strong absorptions at 690710 cm-1 and 730-770 cm-1
t

t Ultraviolet-Visible Spectra of Aromatic Compounds

l Benzene derivatives give an absorption band of

moderate intensity near 205 nm and a less intense band at 250-275 nm

Disubstituted benzenes show the following absorptions

t Mass Spectra of Aromatic Compounds

l The major ion in the mass spectrum of alkyl benzenes is

m/z 91, which corresponds to a benzyl cation (C 6H5CH2+), which rearranges to a tropylium ion (C7H7+) l Another common ion is the phenyl cation (C 6 H 5+)