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Benzena Dan Aromatisitas
Benzena Dan Aromatisitas
1
• Benzene does react with bromine, but only in the presence of
FeBr3 (a Lewis acid), and the reaction is a substitution, not an
addition.
3
Any structure for benzene must account for the following facts:
1. It contains a six-membered ring and three additional
degrees of unsaturation.
2. It is planar.
3. All C—C bond lengths are equal.
The Kekulé structures satisfy the first two criteria but not the
third, because having three alternating bonds means that
benzene should have three short double bonds alternating with
three longer single bonds.
4
• The resonance description of benzene consists of two equivalent
Lewis structures, each with three double bonds that alternate
with three single bonds.
• The true structure of benzene is a resonance hybrid of the two
Lewis structures, with the dashed lines of the hybrid indicating
the position of the bonds.
• 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).
5
• Because each bond has two electrons, benzene has six
electrons.
6
• In benzene, the actual bond length (1.39 Å) is
intermediate between the carbon—carbon single bond
(1.53 Å) and the carbon—carbon double bond (1.34 Å).
7
Draw all possible resonance structures for biphenyl?
8
What orbitals are used to form the indicated bonds, and of
those which is the shortest?
Csp2-Csp2
Csp2-Csp3
Cp-Cp shortest
Csp2-Hs
H
Csp2-Csp2
Csp2-Csp2
Cp-Cp
9
Nomenclature of Benzene Derivatives
10
• There are three different ways that two groups can be
attached to a benzene ring, so a prefix—ortho, meta, or
para—can be used to designate the relative position of
the two substituents.
12
For three or more substituents on a benzene ring:
1. Number to give the lowest possible numbers around the ring.
2. Alphabetize the substituent names.
3. When substituents are part of common roots, name the
molecule as a derivative of that monosubstituted benzene. The
substituent that comprises the common root is located at C1.
13
• A benzene substituent is called a phenyl group, and it can be
abbreviated in a structure as “Ph-”.
14
• The benzyl group, another common substituent that contains a
benzene ring, differs from a phenyl group.
15
Give the IUPAC name for each compound.
PhCH(CH3)2 isopropylbenzene
OH
m-butylphenol
Br
2-bromo-5-chlorotoluene
Cl
16
Which structure matches the given name?
o-dichlorobenzene
Cl
Cl Cl Cl Cl
Cl
Br Cl
A B
C D
C l
C l
17
4-chloro-1,2-diethylbenzene
Cl Cl
Cl
Cl
A B C D
Cl
18
Spectroscopic Properties of Benzene
19
Figure 17.2
13C NMR absorptions
of the three isomeric
dibromobenzenes
20
Give the structure of the compound, C10H14O2, with an IR absorption
at 3150-2850 cm-1. Also has +1H NMR peaks:
1.4 ppm (triplet 6H)
4.0 ppm (quartet 4H)
6.8 ppm (singlet 4H)
2(10)+2-14=8/2=4
IR absorption tells that there are sp2 and sp3 C-H bonds
6.8 ppm tells us its aromatic but with only one type of proton,
what does this tell us?
So aromatic plus 4 DOUS equals benzene ring.
So where would the substituents have to be?
We know we get a doublet of doublets when benzene is para
substituted but with two different groups.
When the substituents are the same what do you get?
21
One type of proton due to symmetry. So we know that we have a
benzen ring with para subsituents that are the same.
X X
O O
22
Stability of Benzene
• 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.
23
Figure 17.6 compares the hypothetical and observed heats of
hydrogenation for benzene.
Figure 17.6
A comparison between the
observed and hypothetical
heats of hydrogenation
for benzene
25
The Criteria for Aromaticity—Hückel’s Rule
Four structural criteria must be satisfied for a compound
to be aromatic.
27
[3] A molecule must be completely conjugated.
Aromatic compounds must have a p orbital on every atom.
28
[4] A molecule must satisfy Hückel’s rule, and contain
a particular number of electrons.
Hückel's rule:
29
Note that Hückel’s rule refers to the number of electrons,
not the number of atoms in a particular ring.
30
Considering aromaticity, a compound can be classified in
one of three ways:
31
Note the relationship between each compound type and a similar
open-chained molecule having the same number of electrons.
32
• 1H NMR spectroscopy readily indicates whether a
compound is aromatic.
• The protons on sp2 hybridized carbons in aromatic
hydrocarbons are highly deshielded and absorb at 6.5-8
ppm, whereas hydrocarbons that are not aromatic
absorb at 4.5-6 ppm.
33
Examples of Aromatic Rings
• Completely conjugated rings larger than benzene are
also aromatic if they are planar and have 4n + 2
electrons.
• Hydrocarbons containing a single ring with alternating
double and single bonds are called annulenes.
• To name an annulene, indicate the number of atoms in
the ring in brackets and add the word annulene.
34
• [10]-Annulene has 10 electrons, which satisfies
Hückel's rule, but a planar molecule would place the two
H atoms inside the ring too close to each other. Thus,
the ring puckers to relieve this strain.
• Since [10]-annulene is not planar, the 10 electrons
can’t delocalize over the entire ring and it is not
aromatic.
35
• Two or more six-membered rings with alternating double and
single bonds can be fused together to form polycyclic aromatic
hydrocarbons (PAHs).
• There are two different ways to join three rings together, forming
anthracene and phenanthrene.
36
What is the correct name for this compound?
A) 3-Nitrotoluene
B) 4-Nitromethylbenzene
C) p-Nitrotoluene
D) (4,1)-Methylnitrobenzene
O 2 N
C) p-Nitrotoluene
37
What is the correct name for this compound?
A) 3,5-difluoroanisole
B) Difluoromethoxybenzene
C) 1,5-difluoro-3-methoxybenzene
D) 1,3-difluoro-5-methyl-O-benzene
F
3,5-difluoroanisole
38
What is the correct name for this compound?
A) 4-bromo-m-xylene.
B) 1-bromo-2,4-dimethylbenzene.
C) p-bromo-m-methyltoluene.
D) o-bromo-m-methyltoluene.
B
r
B) 1-bromo-2,4-dimethylbenzene.
39
Br Br
2 1 3 4
3 6 2 5
4 5 1 6
1,2,4 1,3,4
Br
Br
1 2
1 6
6 3 2 5
5 4
3 4
1,2,5
1,3,6
40
What is the correct name?
A) 1-fluoro-3-isopropyl-5-ethylbenzene
B) 1-ethyl-3-isopropyl-5-fluorobenzene
C) 1-ethyl-3-fluoro-5-isopropylbenzene
D) 1-isopropyl-3-fluoro-5-ethylbenzene
F
C) 1-ethyl-3-fluoro-5-isopropylbenzene
41
Which of these is aromatic?
CH2
A B
43
Indicate which of the following are aromatic and
antiaromatic?
B
A
C is aromatic 4(3)+2=14
A is antiaromatic 4(2)=8
44
• Heterocycles containing oxygen, nitrogen or sulfur, can also be
aromatic.
• With heteroatoms, we must determine whether the lone pair is
localized on the heteroatom or part of the delocalized system.
• An example of an aromatic heterocycle is pyridine.
45
• Pyrrole is another example of an aromatic heterocycle. It
contains a five-membered ring with two bonds and one
nitrogen atom.
• Pyrrole has a p orbital on every adjacent atom, so it is
completely conjugated.
• Pyrrole has six electrons—four from the bonds and two from
the lone pair.
47
Both negatively and positively charged ions can be aromatic if
they possess all the necessary elements.
49
• The tropylium cation is a planar carbocation with three
double bonds and a positive charge contained in a
seven-membered ring.
• Because the tropylium cation has three bonds and no
other nonbonded electron pairs, it contains six
electrons, thereby satisfying Hückel’s rule.
50
Which of the following is aromatic?
A B
C D
A B
D
C
B 8 pi electrons 4(2)=8
53
• Thus far, we have used “valence bond theory” to
explain how bonds between atoms are formed.
• Valence bond theory is inadequate for describing
systems with many adjacent p orbitals that overlap, as
is the case in aromatic compounds.
• Molecular orbital (MO) theory permits a better
explanation of bonding in aromatic systems.
• MO theory describes bonds as the mathematical
combination of atomic orbitals that form a new set of
orbitals called molecular orbitals (MOs).
• A molecular orbital occupies a region of space in a
molecule where electrons are likely to be found.
54
• When forming molecular orbitals from atomic orbitals,
keep in mind that a set of n atomic orbitals forms n
molecular orbitals.
• If two atomic orbitals combine, two molecular orbitals
are formed.
• 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.
55
• The combination of two p orbitals can be constructive—that is,
with like phases interacting—or destructive, that is, with
opposite phases interacting.
Figure 17.8
Combination of two p orbitals
to form π and π* molecular
orbitals
57
• The molecular orbital description of benzene is much
more complex than the two MOs formed in Figure 17.8.
• Since each of the six carbon atoms of benzene has a p
orbital, six atomic p orbitals combine to form six
molecular orbitals as shown in Figure 17.9.
The six MOs are labeled 1- 6, with 1 being the lowest
energy and 6 being the highest.
• The most important features of the six benzene MOs are
as follows:
The larger the number of bonding interactions, the
lower in energy the MO.
The larger the number of nodes, the higher in energy
the MO.
58
• The most important features of the six benzene MOs
(continued):
• The larger the number of bonding interactions, the lower in
energy the MO.
• The larger the number of nodes, the higher in energy the
MO.
• Three MOs are lower in energy than the starting p orbitals,
making them bonding MOs, whereas three MOs are higher
in energy than the starting p orbitals, making them
antibonding MOs.
• 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).
59
Consider benzene. Since each of the six carbon atoms in benzene
has a p orbital, six atomic p orbitals combine to form six MOs.
Figure 17.9
The six molecular orbitals
To fill the MOs, the of benzene
six electrons are
added, two to an
orbital. The six
electrons
completely fill the
bonding MOs,
leaving the anti-
bonding MOs
empty. All bonding
MOs (and HOMOs)
are completely
filled in aromatic
compounds. No
electrons occupy
antibonding MOs.
60
The Inscribed Polygon Method of Predicting Aromaticity
61
• 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.
• The inscribed polygon method is consistent with Hückel's 4n + 2
rule—there is always one lowest energy bonding MO that can
hold two electrons and the other bonding MOs come in
degenerate pairs that can hold a total of four electrons.
62
Figure 17.10
Using the inscribed polygon
method for five- and seven-
membered rings
63
• For the compound to be aromatic, these MOs must be
completely filled with electrons, so the “magic numbers” for
aromaticity fit Hückel’s 4n + 2 rule.
Figure 17.11
MO patterns for cyclic,
completely conjugated systems
64