Broad Classification of Hydrocarbons

Aliphatic compounds: open-chain compounds and ring compounds (that

are chemically similar to open-chain compounds).
E.g., Alkanes, alkenes, alkynes, dienes, alicyclics, etc.

Aromatic compounds: unsaturated ring compounds that are far more

stable than they should be and exhibit special chemical properties
i.e., resist the addition reactions typical of unsaturated aliphatic
compounds.
Original classification was based on aroma (= smell)
Benzene and related compounds.
 Aromaticity and Aromatic Compounds
Aromaticity: Extra stability possessed by a molecule that meets specific criteria

➢ In the nineteenth century, many compounds having properties similar to those of

benzene were isolated from natural sources. Since these compounds possessed
strong and characteristic odors, they were called aromatic compounds.
➢ It should be noted, however, that it is their chemical properties, and not their
odor, that make them special.

4
 Benzene
➢ Benzene (C6H6) is the simplest aromatic hydrocarbon (or arene).
➢ Isolated in 1825 by Michael Faraday
 Benzene
➢ Benzene has four degrees of unsaturation by formula, making it a highly
unsaturated hydrocarbon.
 Benzene Reactivity
➢ Does not react like unsaturated hydrocarbons such as alkenes, alkynes and
dienes i.e., No addition reactions
 Reactions of benzene: substitutions
➢ Benzene does react but only in the presence of promoter/catalysts
and the reaction is a substitution of ‘H’, not an addition.

1. Nitration
C6H6 + HNO3, H2SO4 → C6H5NO2 + H2O
2. Sulfonation
C6H6 + H2SO4, SO3 → C6H5SO3H + H2O
3. Halogenation
C6H6 + X2, Fe → C6H5X + HX
4. Freidel-Crafts alkylation
C6H6 + RX, AlCl3 → C6H5R + HX
 Kekulé di-Substituted benzenes

➢ But having three alternating  bonds means that benzene should have three
short double bonds alternating with three longer single bonds.

➢ In benzene all C—C bond lengths are equal and is 1.39 Å (by X-ray analysis) 9
Any Proposed structures of benzene must account for

1. a six-membered ring and three additional degrees of

unsaturation.
2. Planar.
3. From X-ray All C—C bond lengths are equal (1.39 Å) , and
intermediate in length between single (1.54 Å) and double
bonds (1.34 Å) .

In addition,
Its lack of reactivity towards electrophilic addition.

10
 New representation
• Later Kekule proposed the structure of benzene as a resonance
hybrid of the two Lewis structures, with the dashed lines of the
hybrid indicating the delocalization of the  bonds. This fits well
with the requirements
• We will use one of the two Lewis structures and not the hybrid in
drawing benzene. This will make it easier to keep track of the
electron pairs in the  bonds (the  electrons).
• Because each  bond has two electrons, benzene has six 
electrons.

12
Stability of Benzene and Aromaticity

13
Stability of Benzene and Aromaticity

1 kcal = 4.18 kJ

i.e., low lying-in energy 14

 Stability of Benzene and Aromaticity
➢ Consider the heats of hydrogenation of cyclohexene, 1,3-cyclohexadiene
and benzene, all of which give cyclohexane when treated with excess
hydrogen in the presence of a metal catalyst.

1 kcal = 4.18 kJ

15
 Resonance Energy

➢ The low heat of hydrogenation of benzene means that benzene is

especially stable—even more so than conjugated polyenes.
➢ This unusual stability is characteristic of aromatic
compounds.
16
Resonance Energy

17
 Delocalization / Resonance Energy
➢ The huge difference between the hypothetical and observed
heats of hydrogenation for benzene cannot be explained solely
based on resonance and conjugation but by delocalization.

18
Delocalization/ Resonance Energy

19
Delocalization/ Resonance Energy

How can we explain this? 20

 Molecular Orbitals Theory

➢ Molecular orbital (MO) theory permits a better

explanation of bonding in aromatic systems.
➢ When forming molecular orbitals from atomic orbitals, keep in
mind that a set of n atomic orbitals forms n molecular orbitals.
➢ Recall that aromaticity is based on p orbital overlap.
➢ Also note that the two lobes of each p orbital are opposite in
phase, with a node of electron density at the nucleus.
➢ When two p orbitals combine, two molecular orbitals should
form.

21
 Molecular Orbitals Theory

➢ In the quantum mechanical model of the atom, a nodal plane is a region around
the nucleus where the probability of finding an electron is zero or almost zero. 22
 Molecular Orbitals Theory

• The two pairs of MOs with the same energy are called
degenerate orbitals.

• The highest energy orbital that contains electrons is called the

highest occupied molecular orbital (HOMO).

• The lowest energy orbital that does not contain electrons is

called the lowest unoccupied molecular orbital (LUMO).

23
 Molecular Orbitals Theory
The combination of two p orbitals can be
➢ constructive: with like phases reinforcing, or
➢ destructive: with opposite phases cancelling.

➢ When two p orbitals of similar phase overlap side-by-side, a 

bonding molecular orbital results.
➢ When two p orbitals of opposite phase overlap side-by-side, a
* antibonding orbital results. 24
Molecular Orbitals Theory

25
Molecular Orbitals Theory

26
Molecular Orbitals Theory

27
 Molecular Orbitals of Benzene:

➢ Since each of the six carbon atoms of benzene has a p orbital,

six atomic p orbitals combine to form six  molecular orbitals

➢ The six MOs are labeled 1- 6, with 1 being the lowest energy
and 6 being the highest.

➢ A greater number of bonding interactions gives a lower MO

energy.

➢ A greater number of nodes, gives a higher MO energy.

➢ In the quantum mechanical model of the atom, a nodal plane is a region around
the nucleus where the probability of finding an electron is zero or almost zero. 28
 Molecular Orbitals of Benzene:
1: zero nodes
2 and 3: one node
To fill the MOs, the six
electrons are added, 4 and 5: two nodes
two to an orbital. The 6: three node
six electrons completely
fill the bonding MOs,
leaving the anti-bonding
MOs empty.

non-bonding MOs
All bonding MOs (and
HOMOs) are completely
filled in aromatic
compounds.
No  electrons occupy
antibonding MOs.

29
 Molecular Orbitals of Benzene:

➢ In the quantum mechanical model of the atom, a nodal plane is a region around
the nucleus where the probability of finding an electron is zero or almost zero. 30
Molecular Orbitals of Benzene:

31
Benzene vs. 1,3,5-hexatriene (acyclic)

32
Molecular Orbitals of Cyclobutadiene

33
Is there an easy way to draw Molecular Orbital picture?

The Inscribed Polygon Method (Frost Diagram) for Predicting

MO’s

34
The Inscribed Polygon Method (Frost Diagram) for Predicting
MO’s and Aromaticity

35
The Inscribed Polygon Method (Frost Diagram) for Predicting
MO’s and Aromaticity

• This method works for all monocyclic completely conjugated systems

regardless of ring size.
• The total number of MOs always equals the number of vertices of the polygon.

36
The Inscribed Polygon Method (Frost Diagram) for Predicting
MO’s and Aromaticity

37
Other Examples

38
The Inscribed Polygon Method (Frost Diagram) for Predicting
MO’s and Aromaticity

39
 The Criteria for Aromaticity
Four structural criteria must be satisfied for a compound
to be aromatic.

[1] A molecule must be cyclic.

➢ To be aromatic, each p orbital must overlap with p orbitals on

adjacent atoms.
40
[2] A molecule must be planar.
➢ All adjacent p orbitals must be aligned so that the  electron
density can be delocalized.

➢ Since cyclooctatetraene is non-planar, it is not aromatic, and it

undergoes addition reactions just like those of other alkenes.

41
[3] A molecule must be completely conjugated.

➢ Aromatic compounds must have a p orbital on every atom.

42
[4] A molecule must satisfy Hückel’s rule, and contain
a particular number of  electrons.

Hückel's rule:

➢ Benzene is aromatic and stable because it contains 6  electrons.

➢ Cyclobutadiene is antiaromatic and unstable because it contains
4  electrons.

43
Note: Hückel’s rule refers to the number of  electrons, not the
number of atoms in a particular ring.

E.g., Furan, thiophene, pyrrole, cyclopentadienyl

anion, cycloheptatrienyl cation
44
Considering aromaticity, a compound can be classified in
one of three ways:

1. Aromatic—A cyclic, planar, completely conjugated compound with 4n +

2  electrons.
2. Antiaromatic—A cyclic, planar, completely conjugated compound with
4n  electrons.
3. Not aromatic (nonaromatic)—A compound that lacks one (or more) of
the following requirements for aromaticity: being cyclic, planar, and
completely conjugated.

Stability: Aromatic >> Nonaromatic > AntiaromaticCompounds

45
Note the relationship between each compound type and a similar
open-chained molecule having the same number of  electrons.

46
 The Basis of Hückel’s Rule:

• Why does the number of  electrons determine whether a

compound is aromatic?
• The basis of aromaticity can be better understood by
considering molecular orbital theory as we have seen earlier

48
For the compound to be aromatic, these bonding MOs must be
completely filled with electrons, so the “magic numbers” for aromaticity
fit Hückel’s 4n + 2 rule.

MO patterns for cyclic, completely conjugated systems

49
Cyclopropenyl cation

H 2 3
4n+2=2
1 n=0
H H
aromatic
cycloprop enyl cation
2 -electrons
Cyclopentadienyl cation
H
4 5
H H 4n=4
2 3 n=1
H H
anti-aromatic
cyclopentad ienyl cation 1
4 -electrons

Cycloheptatrienyl cation
6 7
H H
4 5 4n+2=6
H H
n=1
2 3
H H aromatic
H 1
cycloheptatrienyl cation
6 -electrons 50
Cyclopropenyl anion
H H H
+ B: + B:H
4n=4
H H H H
n=1
cyclopropenyl anion
anti-aromatic
4 -electrons

2 3

1

Cyclopentadienyl anion
H H H
H H H H
+ B: + B:H
4n+2=6
H H H H
n=1
pKa ~ 16 cyclopentad ienyl anion aromatic
6 -electrons
4 5

2 3
1 51
 Annulenes
➢ Annulene's are the family of completely conjugated, monocyclic
hydrocarbons
➢ The annulenes are named as [n]-annulene where n is an even number
that represents the number of C atoms in the ring.
➢ We have already met the first 3 members of the series, [4]-, [6]-, and [8]-
annulene but we called them cyclobutadiene, benzene and cycloocta-
tetraene respectively.
➢ Higher members of the annulene series have also been synthesized and
investigated in relation to their aromaticity.
➢ Remember that according to the Huckel rule, (4n + 2) π electrons
systems are expected to aromatic whereas 4n π electrons systems are
not.
 Annulenes

[4]-annulene (anti-aromatic) [6]-annulene (aromatic) [8]-annulene (non-aromatic)

cyclobutadiene
Benzene
➢ Tub shape, not planar

[10]-annulene 10 -electrons H H
(non-aromatic) 4n+2 = 10, n=2.
H H
H
H
H H
H H

➢ Unstable in-plane, because of H-H repulsive stain.

➢ Goes out of plane.

Naphthalene
➢ Stable because of locked geometry
12 -electrons
4n=12, n=3

14 -electrons; 4n+2=14, n=3

54
 16 -electrons; 4n=16, n=4
(not planar)

18 -electrons; 4n+2=18, n=4

55
56
57
58
59
60
Some common observations on compounds

H Cl H
+ AgBF4 BF4 + AgCl
H H H H

H Cl H

H H H H
+ AgBF4 BF4 + AgCl
H H H H

H H H
pKa ~ 16
H H H H
+ H 2O + H 3O +
H H H H

H
H Br
H H H H

H H Br -
H H
H H 61
H H
Resonance Energy (Kcal/mol)
 Other forms of Carbon

➢ The two most common elemental forms of carbon are diamond and
graphite.
➢ Their physical characteristics are very different because their
molecular structures are very different.

63
 Buckminsterfullerene: Is it Aromatic?

➢ 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.

64
 Anti-aromatic compounds and Ions

4- electron system

cyclobutadiene cyclopropenyl
anion Cyclopentadienyl
cation

8- electron system

cyclooctatetraene cycloheptatrienyl Pentalene
anion

12- electron system

heptalene
 Homoaromaticity
➢ Homoaromatic compounds possess an interrupted π system but display thermodynamic
stability and many of the spectroscopic, magnetic, and chemical properties associated
with aromatic compounds, due to through-space or through-bond interactions.
➢ This formal discontinuity is apparently bridged by p-orbital overlap, maintaining a
contiguous cycle of π electrons that is responsible for this preserved chemical stability.

➢ Positive homoaromatic
species are well known.

➢ In some cases, the conjugation is interrupted by a sp3 hybridized carbon atom.

E.g., cyclooctatrienyl cation (homotropylium ion)
➢ Six electrons are
spread over seven
carbon atoms as in
tropylium cation.
NMR Spectroscopy
 NMR Spectroscopy
➢ NMR is the most powerful tool available for structural determination.

➢ It is used to study a wide variety of nuclei: 1H; 13C; 15N; 19F; 31P

NMR Spectroscopy
Where is it?

1nm 10 102 103 104 105 106 107

(the wave) X-ray UV/VIS Infrared Microwave Radio

Frequency
(the transition) electronic Vibration Rotation Nuclear
(spectrometer) X-ray UV/VIS Infrared/Raman NMR
Fluorescence
 Before using NMR
What are N, M, and R ?

Properties of the Nucleus

Nuclear spin
Nuclear magnetic moments

The Nucleus in a Magnetic Field

Precession and the Larmor frequency
Nuclear Zeeman effect & Boltzmann distribution

When the Nucleus Meet the right Magnet and radio wave
Nuclear Magnetic Resonance
69
 Nuclear Spin
➢ Nuclear spin is characterized by a quantum number I, which may be integer,
half-integer or 0.
➢ Only nuclei with spin quantum number I ≠ 0 can absorb/emit electromagnetic
radiation.
➢ Nuclei are positively charged spherical spinning objects, which is like tiny magnet.
➢ Nuclear magnetic moments : The circulation of nuclear charge would generate
a magnetic moment along the spin axis

Magnetic moment  is another important parameter for a nuclei

 =  I (h/2)
I = spin number (1/2; 1; 3/2 etc) ; h = Plank’s constant (6.626 × 10-34 kJ/mol)
 = gyromagnetic ratio (property of a nuclei)
1H: I=1/2 ,  = 267.512 *106 rad T-1S-1
(2I+1) spin orientations
13C: I=1/2 ,  = 67.264*106
possible for a nuclei
15N: I=1/2 ,  = 27.107*106
with spin number I
(2I+1) spin orientations possible for a nuclei with spin number I
(proton)

E and
Magnet Strength
The energy difference between the two spin states depends
on the strength of the magnetic field

randomly
oriented nuclei
(no magnetic field)

➢ In a 1.41 T field, a 60
MHz photon is required
to flip a proton.
 Diamagnetic Shielding
➢ If all protons absorbed the same amount of energy in a given magnetic
field, not much information could be obtained.

➢ What makes it useful is that different protons usually appear at different

chemical shifts (d).

➢ So, we can distinguish one kind of proton from another.

Why do we see separate signals??

Ethanol = CH3CH2OH
 Diamagnetic Shielding

➢ Why do different protons appear at different chemical shift values (d) ?

➢ The main reason is shielding by electrons.

➢ The electrons in a bond (-bond or s-bond) shield the nuclei from the magnetic
field.

➢ So, if there is more electron density around a proton, it sees a slightly lower
magnetic field, less electron density means it sees a higher magnetic field

This represents the electron density of a C-H bond. How much electron
Z density is on the proton depends on what else is attached to the carbon. If Z
C H is an elelctronegative atom, the carbon becomes electron deficient and pulls
some of the electron density away from the H. if Z is an electron donating
group, more electron density ends up on the H.
 Diamagnetic Shielding
➢ How do the electrons shield the magnetic field?
➢ By moving or circulating. Can be represented
➢ Moving or circulating electrons create an induced as Beff = Bo( 1 - s )
magnetic field (secondary field) that opposes the
external applied magnetic field of our NMR
machine.
➢ So, the magnetic field (the effective field
strength Beff) felt by the nucleus is always less
than the applied filed strength (Bo) and is
dependent on the surrounding groups and atoms.
➢ It’s not a huge effect, but it’s enough to enable us
to distinguish between different protons in our
sample.
 CH3
H3C Si CH3 Tetramethylsilane (TMS)
CH3

➢ TMS is added to the sample.

➢ Signal defined as zero.

➢ Since silicon is less electronegative than carbon, TMS protons are highly

shielded.

➢ In general, organic protons absorb at higher frequency (to the left) than

the TMS signal and give positive chemical shift (d).

➢ There are protons which absorb at lesser frequency (to the right) than the

TMS signal and give negative chemical shift (d).

 Properties of Some Deuterated NMR Solvents

Residual Residual
Solvent B.P. °C 1H signal (δ) 13C signal (δ)

acetone-d6 55.5 2.05 ppm 206 & 29.8 ppm

acetonitrile-d3 80.7 1.95 ppm 118 & 1.3 ppm

benzene-d6 79.1 7.16 ppm 128 ppm

chloroform-d 60.9 7.27 ppm 77.2 ppm

cyclohexane-d12 78.0 1.38 ppm 26.4 ppm

dichloromethane-d2 40.0 5.32 ppm 53.8 ppm

dimethylsulfoxide-d6 190 2.50 ppm 39.5 ppm

nitromethane-d3 100 4.33 ppm 62.8 ppm

150, 135.5 & 123.5

pyridine-d5 114 7.19, 7.55 & 8.71 ppm
ppm

tetrahydrofuran-d8 65.0 1.73 & 3.58 ppm 67.4 & 25.2 ppm
NMR Machine
NMR Machine
 shielding

deshielding

shielding deshielding
shielding

deshielding deshielding
shielding shielding

Homoaromaticity

shielding

Ha = -0.3 ppm
deshielding
Hb = 5.1 ppm
H1 & H7 = 6.1 ppm
H2-H6 = 8.5 ppm
 ➢ Paratropic
behaviour
(paramagnetic
ring current)

shielding

deshielding deshielding

deshielding

shielding

shielding
Temperature effect
Temperature effect
 Two Energy States for proton
➢ The magnetic fields of the spinning nuclei will align either with the
external field, or against the field.
➢ A photon with the right amount of energy can be absorbed and cause
the spinning proton to flip.

(2I+1) spin orientations possible for a nuclei with spin number I