Introduction to Organic Chemistry
©Rohen Prinsloo, Department of Chemistry, University of Calgary 1
What is “Organic Chemistry” ?
Organic chemistry
▪ Chemistry of compounds of CARBON
▪ Only 1 in 625 atoms is carbon (0.16%)
( 1 in 2.07 (48.5%) is oxygen)
▪ Carbon has ability to form bonds with itself
▪ Approx. 10,000,000 known compounds, ~ 90% organic
©Rohen Prinsloo, Department of Chemistry, University of Calgary 2
Organic Chemistry - History
• Until the 19th century – organic molecules come from living
things (vital force theory)
• In 1828, Friederich Wohler synthesized urea (organic) from
ammonium cyanate (inorganic)
ammonium urea
cyanate
http://en.wikipedia.org/
wiki/File:Friedrich_W%
C3%B6hler_Stich.jpg
©Rohen Prinsloo, Department of Chemistry, University of Calgary 3
Determine Molecular formula
Justis Liebig Jons Jakob Berzelius Jean B. A. Dumas Stanislao Cannizzaro
18th Century
1. Quantitative methods for determining chemical composition by J. Liebig, J. J.
Berzelius, and J. B. Dumas. The chemical analyses could only provide empirical
formulas – ratio of elements
2. In 1860, Cannizzaro reported that although ethylene, cyclopentane and
cyclohexane all have a common empirical formula (CH2) , their molecular
formulas are C2H4, C5H10 and C6H12 respectively.
©Rohen Prinsloo, Department of Chemistry, University of Calgary 4
Structural Theory of Organic Chemistry
August Kekulé Archibald Couper Alexander Butlerov
Between 1858-1961
▪ Independent work by A. Kekulé, A. Couper and A. Butlerov laid down the
basis of structural theory in organic chemistry
▪ The number of BONDS to different elements in organic compounds was
deduced. These are VALENCIES
©Rohen Prinsloo, Department of Chemistry, University of Calgary 5
Structural Theory of Organic Chemistry
Multiple bonds are possible for carbon - all maintain its tetravalency
The development of a structural theory, attention to the linkages
among atoms (BONDs), solved the problem of ISOMERISM.
Constitutional isomerism: different ways to link atoms for the
same molecular formula.
©Rohen Prinsloo, Department of Chemistry, University of Calgary 6
Isomerism
▪ Two isomers could exist for molecular formulae: C2H6O
Ethanol Dimethyl Ether
Boiling Point 78.5 °C -24.9 °C
Melting Point -117.3 °C -138 °C
Reaction with Na Yes No
©Rohen Prinsloo, Department of Chemistry, University of Calgary 7
Evolution of Chemical Information
Ethanol and dimethyl ether have same molecular formulae but differ in how the
atoms are connected. They are CONSTITUTIONAL ISOMERS.
Molecules A. Determine the relationship of the
Same molecular formulae? following with the one in the box
no yes
Not Isomers
isomers Differ by atom
connectivity?
no yes
Stereoisomers Constitutional
• Same atom connectivity
• differ in 3D projections
Isomers
• Differ in atom connectivity
©Rohen Prinsloo, Department of Chemistry, University of Calgary 8
Organic Chemistry and the Periodic Table
• Organic chemistry is the chemistry of the covalent compounds
of CARBON
What about non-carbon or hydrogen atoms?
• Other elements in organic chemistry are called heteroatoms
• O, N, S, Si, P, B, F, Cl, Br, I
• Heteroatoms are the basis of functional groups – generally the
reactive portion of organic molecules
©Rohen Prinsloo, Department of Chemistry, University of Calgary 9
Organic Chemistry and the Periodic Table
©Rohen Prinsloo, Department of Chemistry, University of Calgary 10
Functional Group vs Mechanistic
Methods for learning Organic Chemistry
▪ Functional group approach
▪ connects different reactions of similar systems
▪ convenient organisation
▪ promotes memorisation
▪ Mechanistic approach
▪ facilitates defining HOW and WHY things happen
▪ reduces the need to memorise
▪ promotes the recognition of similarities
▪ facilitates rationalising new examples
▪ initially difficult for students
©Rohen Prinsloo, Department of Chemistry, University of Calgary 11
Chemistry fundamentals
What do you need to know from GENERAL CHEMISTRY to be
able to tackle the mechanistic approach ?
▪ atomic and molecular structure
▪ VSEPR
▪ hybridisation
▪ fundamental rules of valence
▪ formal charges
▪ Lewis structures
▪ acidity and basicity
▪ resonance
▪ electronegativity
▪ isomerism
©Rohen Prinsloo, Department of Chemistry, University of Calgary 12
Chemistry fundamentals
What are the KEY CONCEPTS you need to master in ORGANIC
CHEMISTRY in order to be able to tackle the mechanistic
approach ?
▪ nucleophilicity
▪ electrophilicity
▪ leaving groups
▪ functional group recognition
▪ intermediates e.g. carbocations, carbanions, radicals
▪ curly arrows
▪ resonance
▪ inductive effects
▪ acidity and basicity
©Rohen Prinsloo, Department of Chemistry, University of Calgary 13
Terminology
Electronegativity
▪ The ability of an atom (or a group of atoms) to attract electrons
towards itself
Functional group
▪ An atom (or a group of atoms) in a molecule that defines
characteristic reactivity under a particular set of reaction
conditions
Mechanism
▪ A schematic diagram that shows how each step in a reaction
occurs and accounts for all the bonding changes during that
reaction
Resonance
▪ The delocalisation of p electrons to give an alternate but viable
Lewis structure
©Rohen Prinsloo, Department of Chemistry, University of Calgary 14
Terminology
Nucleophile
Nucleus loving, hence electron rich, electron donor, Lewis base
Nucleophilicity
How nucleophilic is a nucleophile?
Electrophile
Electron loving, hence electron poor, electron acceptor, Lewis acid
Electrophilicity
How electrophilic is an electrophile?
Leaving group
An atom (or a group of atoms) that is displaced with the bonding
electrons
©Rohen Prinsloo, Department of Chemistry, University of Calgary 15
Symbolism
Structural representations
Mastering line diagrams is a key part of the deciphering the “code” of organic
chemistry
Line diagrams are a “shorthand” to represent structures efficiently
Rules:
1. Each node is a C atom unless indicated otherwise.
2. Don’t show H atoms attached to C atoms
3. Must show H atoms attached to other atoms e.g. N and O
CH3CH2CH3
CH3CH2OH
©Rohen Prinsloo, Department of Chemistry, University of Calgary 16
Arrows used in Organic Chemistry
Reaction of A to give B
Equilibrium of A with B
Resonance of A and B
©Rohen Prinsloo, Department of Chemistry, University of Calgary 17
Arrows used in Organic Chemistry
Mechanistic curly arrows:
a) motion of a pair of e-
bond making
bond breaking
b) motion of a single e-
bond making
bond breaking
©Rohen Prinsloo, Department of Chemistry, University of Calgary 18
Curly Arrows
THE KEY TO UNDERSTANDING ORGANIC CHEMISTRY !
They are used to describe mechanisms
Why are they important ?
knowing where e- are and how they are moving accounts for
the bonding changes and hence reactions
Remember that a covalent bond is a pair of e-
Always draw curly arrows from electron rich to electron poor
©Rohen Prinsloo, Department of Chemistry, University of Calgary 19
Interesting Organic Molecules
Urea (1828) Acetic acid (1845) Camphor (1903)
Quinine (1944)
Strychnine (1954)
Taxol TM (1994)
©Rohen Prinsloo, Department of Chemistry, University of Calgary 20
Interesting Organic Molecules
Aspirin Caffeine Saccharin
Penicillin CT
Morphine R = H
Codeine R = CH3
©Rohen Prinsloo, Department of Chemistry, University of Calgary 21
Modern Materials are Based on Organic
Chemistry
▪ Various plastics such as polyvinyl chlorides (PVC), polypropylenes (PP),
polyethylenes (PE), polystyrenes (PS), polyurethanes (PU), and other polymers
such as Teflon, polyacrylates, nylons etc. are carbon based.
polystyrenes
polyvinyl
polypropylenes chlorides
polyacrylates
polyethylenes
Teflon
nylons
polyurethanes
paints
©Rohen Prinsloo, Department of Chemistry, University of Calgary 22
