CY 1001 –Organic Chemistry

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 Resources:
Text Books:
1. J. Mc Murray, ‘Organic Chemistry’, Brooks/Cole Publishing Co., 5th Edition,2003.

2. P. Bruice, ‘Organic Chemistry,’ Prentice Hall, New Delhi, 3rd Edition, 2001.
3. K. P. C. Vollhardt & N. E. Schore, ‘Organic Chemsitry’. Structure and Function’,
Freeman Press, 4th Edition, 2003
4. F. Carey, ‘Organic Chemistry’, McGraw Hill Publishers, 5th Edition, 2001
5. R. T. Morrison & R. N. Boyd, ‘Organic Chemistry’, Prentice Hall, New Delhi, 6th
Edition, 1999.
Web Resource:
http://nptel.ac.in/courses/122106029/1
Video Courses: http://academicearth.org/chemistry/ - see Prof. Peter-Vollhardt
lectures

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Importance
OLEDS Dyes Polymer

BCP
PET

Medicine Opthalmic Lenses

Tamoxifen

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Organics
Organic Compounds

Aromatic Alipha,c

Aroma - smell Fat Like

Time

Associated with stability now

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Benzene - History
1825 Isolated a pure compound from fuel
used to burn gaslights (Whale fat oil)

Analysis showed 1:1 H/C ratio

Faraday Structure?

1834 Isolated same compound from gum benzoin

Called it Benzene

Analysis showed 1:1 H/C ratio

MW 78 C6H6

Structure? Ø Degree of unsaturation

Mitscherlich is Four
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 Kekule – Solved the Benzene Puzzle (1865)
Ø Possible structures:

Ø Kekule proposed the cyclic conjugated triene for

benzene
Kekule (1829-1896) Ø Reactivity did not match with conjugated triene!
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 Reactivity of Benzene
Br
C6H 6 H
No reaction
C6H5Br Br 2
FeBr3 H
Br2/FeBr3 Br

Ø Expected 4 products, but obtained only 3 products!

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Mystery continues…
From X-ray and electron diffraction analysis:
• Benzene is planar
• All bonds are of same length (1.397 Å)
C-C is 1.54 Å and C=C is 1.33 Å

• Carbon nuclei are posiHoned at equal distances. π-electrons are

delocalized with a bond order of 1.5 between adjacent carbons.
This means π-electrons are delocalized.

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Conjugation
• Conjugation is used to describe the situation that occurs when
double bonds (π-system) are “linked together”

• The result of conjugation is the extra bonding interaction between

the adjacent π-system that results to an overall stabilization of the
molecule

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Delocalization/Resonance
• Delocalization is the distribution of electron density beyond a fixed
place such as a single atom, lone pair, or covalent bond

Resonance contributors Resonance hybrid

• Resonance: A condiHon in which a molecule cannot be adequately

represented by a single Lewis structure; two or more Lewis
structures are required.

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Resonance Theory
Rules for Resonance

• Only electrons move around. All nuclei in the same position

• Structures with fewer bonds or greater charge separation not favourable

• For 2 structures with formal charge and same number of bonds :

Negative charge favourable on more electronegative atom
Positive charge favourable on more electroposition atom

• All the groups containing the C=C should be in the same plane

Resonance can explain the properties of Benzene

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Resonance Structures

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ImplicaQons of Resonance
Molar Heats of hydrogenation è Stability

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Resonance
CY1001 energy/ Stabilization = 151 KJ/mol or 36 Kcal/mol
Resonance, Stability and Aromaticity
Cyclic conjugated polyenes with stability due to
resonance delocalization – Aromatic?

Can the huge resonance energy or stabilization be explained only

by conjugation effects?

What about cyclobutadiene?

Cyclobutadiene is highly UNSTABLE!

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Aromaticity – Molecular Orbital Picture
Let us look at the π-bonding interactions closely
The σ – framework can be neglected as it is in the nodal plane

6 × sp2

sp2 orbitals
top view side view π-overlap

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Molecular Orbital (MO) Theory
• MO-theory describes covalent bond formation as resulting from a
mathematical combination of atomic orbital (wave functions) to
form molecular orbitals.
• Molecular orbitals describes a region of space in a molecule where
electrons are most likely to be found. It has specific size, shape and
energy.
Subtractive way

AddiGve way
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MO – π-bond in ethylene
LUMO
(Lowest Unoccupied Molecular Orbital)
Subtractive way

Additive way

HOMO
(Highly Occupied Molecular Orbital)
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Molecular Orbitals: Conjugated Polyenes

§ Orbitals are conserved: ‘n’ atomic orbitals combine to produce

‘n’ molecular orbitals

§ For polyene containing nπ-electrons (n = even number)

• n/2 bonding molecular orbitals
• n/2 antibonding molecular orbitals

§ The lowest energy MO has zero nodes, the next higher has one
node, … and nth MO will have (n-1) nodes

§ The nodal points are found at the symmetric points

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π-MO of 1,3-butadiene

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π-MO of 1,3-butadiene

π4 π4
(LUMO)

Antibonding
π3 π3
(LUMO) (HOMO)
Energy

π2 π2

Bonding
(HOMO)

π1 π1

Ground Excited
s-trans s-cis state state
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PracQce at Home

Draw the molecular orbital diagram and energy

level diagram for 1,3,5-hexatriene and Identify the
HOMO and LUMO

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