1 Benzene
1 Benzene
1 Benzene
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Definition
Molecular structure
Orbital picture
Aromaticity
Nomenclature
Physical properties of benzene
Preparation of benzene and its homologues
Reactions of benzene
Electrophilic Aromatic Substitution reactions
Mechanism
Reactivity
orientation
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Definition
Aromatic compounds
Compounds that resemble benzene in
chemical behavior are known as aromatic
compounds.
They possess a pleasant aroma and so
named aromatic compounds.
Arenes: aromatic hydrocarbons
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Molecular structure of benzene
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DERIVATION OF STRUCTURE
Molecular formula: elemental analysis, molecular weight
determination, C6H6.
This indicated benzene was a highly unsaturated compound.
(n-Hexane C6H14)
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Resonance of benzene
Resonance: The phenomenon in which 2 or more structures can
be written for a substance which involve identical positions of
atom is called resonance.
Spectroscopic measurements show
Benzene is a planar molecule
C-C bonds are of equal length, 1.40 A. (C-C 1.54A, C=C 1.34A)
Resonance hybrid is more stable than any of its resonatic
structures.
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Orbital structure
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All six C Atoms are sp2 Hybridized. The sp2 hybrid orbitals
overlap with each other and with s orbitals of the six H
atoms forming C-C and C-H sigma bonds.
All Bond angles are 1200
C-C bond length 1.40 A, all same.
C-H bond length 1.08 A
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Formation of p molecular orbital in benzene
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Criteria for Aromaticity
There must be an uninterrupted ring of p orbital-bearing
atoms leading to a delocalized p cloud.
4. Huckel rule
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[1] A molecule must be cyclic.
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[3] A molecule must be completely conjugated.
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[4] A molecule must satisfy Hückel’s rule, which
requires a particular number of p electrons.
Huckel rule
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Cyclobutadiene is antiaromatic and especially unstable
because it contains 4 p electrons.
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Hückel’s Rule
Note that Hückel’s rule refers to the number of p electrons, not
the number of atoms in a particular ring.
No. of p electrons that
satisfy the rule.
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With regard to aromaticity, a compound can be
classified in one of three ways:
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Note the relationship between each compound type and a similar
open-chained molecule having the same number of p electrons.
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Annulenes
A completely conjugated, monocyclic
hydrocarbon is called an annulene
(not necessarily aromatic).
To name an annulene, indicate the
number of atoms in the ring in
brackets and add the word annulene.
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nonaromatic
It is cyclic but not plan
ar(tub shaped)
8 p electrons
4n+2=8, 4n=6, n=1.5
(not integer)
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Aromaticity
The criteria for aromaticity also can be applied
to polycyclic hydrocarbons
Naphthalene (n=2, 5 pairs of p electrons),
phenanthrene (n=3, 7 pairs of p electrons), and
chrysene (n=4, 9 pairs of p electrons) all are
aromatic.
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Heterocyclic Compounds
• Heterocycles containing oxygen, nitrogen or
sulfur, can also be aromatic.
• With heteroatoms, one must determine
whether the lone pair is localized on the
heteroatom or part of the delocalized p
system.
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Pyrrole
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6 parallel p orbitals containing 6 ele. Form a delocalized
p molecular orbital.
Unused sp2 orbital of N containing 2 nonbonding ele.
Remains as such.
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Heterocyclic Compounds
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Nomenclature of Benzene Derivatives
• Alkyl benzene: To name a benzene ring with one
substituent, name the substituent and add the word
benzene.
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• There are three different ways that two groups can be
attached to a benzene ring, so the prefixes: ortho, meta,
or para are used to designate the relative position of the
two substituents.
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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.
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• Other common monosubstituted benzenes:
benzaldehyde, benzoic acid, acetophenone & styrene
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• A benzene substituent is called a phenyl group, and
it can be abbreviated in a structure as “Ph-”.
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• The benzyl group, another common substituent
that contains a benzene ring, differs from a
phenyl group.
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Physical properties
Colourless liquid
Solubility
Insol. In water
Miscible with alcohol, ether and chloroform
Good solvent for many inorganic and organic substances like fat, resin,
sulphur, iodine
With polar grp: moderately sol. In water ex. Benzoic acid
More than 1 OH grp: sol. In water ex. Resorcinol
Density
Less dense than water
Halogenated benzenes are denser than water
M.p.
High m.p. than alkane as they are more symmetrical
Para has high m.p. than ortho and meta
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Physical properties
Vapors: highly toxic which on inhalation produce loss of
consciousness.
It burns with a luminous sooty flame. Alkanes and alkenes: burn with a
bluish flame
B.p. 80.1
ortho has high b.p. than meta (low dipole moment) and para
(symmetrical) as ortho has high dipole moment.
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