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MSE245
Organic Materials
Chemistry and Processing
Professor Naomi Matsuura
WB 138
naomi.matsuura@utoronto.ca
January 10, 2024
1
Weekly Timetable
Monday Tuesday Wednesday Thursday Friday
TUT LEC
9:00-10:00
GB221 GB303
LAB
LM117
10:00-12:00
LEC
15:00-17:00
GB303
TUT: tutorial, LEC: Lecture, LAB: Laboratory exercise, Office hours: By appointment
2
Teaching staff
Instructor: Prof. Naomi Matsuura
(naomi.matsuura@utoronto.ca)
Instructor (Lab): Prof. Kai Huang

(nanokai.huang@utoronto.ca)
Lab TA: Mr. Raunaq Bagchi

(r.bagchi@mail.utoronto.ca)
Tutorial TA: Mr. Sam Penner

(samuel.penner@mail.utoronto.ca)
3
MSE 245 Organic Chemistry Grading
• 2 lectures per week (3 hours total)

• A total of 3 labs (6% each)* 18%
• Safety and 3 pre-lab quizzes 5%
• 1 hour tutorial per week (Best 8 assignments) 12%
• Two term tests*
(Tentative dates: Feb. 9 and March 15, 15% each) 30%
• Final exam: TBD 35%
Total 100%
*These components are required as part of this course 4
Textbook (Required)
Organic Materials Chemistry

and Properties”,
ISBN 9781119383673
This is a custom textbook, only

available at the U of T bookstore
5
Lab Schedule (Mandatory)
• First in-person lab scheduled for January 15, 2024
• Mondays (9:00 -12:00), LM117
• Class is divided into 3 groups (Carbon, Hydrogen and
Oxygen)
• 3 labs total:
• Lab 1: Jan 15 (C); Jan 22 (H); Jan 29 (O)
• Lab 2: Feb 5 (C); Feb 12 (H); Feb 26 (O)
• Lab 3: Mar 4 (C); Mar 11 (H); Mar 18 (O)
• Pre-lab quizzes (Jan 8, Jan 11, Feb 1, Feb 29)
6
Course structure
• If there are any outstanding questions not answered during

class, please use the “muddiest point” discussion forum in
Quercus
• Depending on the day (Wednesday or Friday), points requiring
clarification will be re-addressed during the first few minutes
of the next class and/or at the beginning of the tutorial
• Tutorial assignments (due on Thursdays at the beginning of
the tutorial period) will cover material up to the previous
Friday’s class
7
ORGANIC MATERIALS
CHEMISTRY & PROCESSING
WHY SHOULD WE CARE?
8
What is materials science?
https://en.wikipedia.org/wiki/Materials_science
CREATION AND INVENTION OF NEW MATERIALS WITH

DESIGNED PROPERTIES THAT DO NOT EXIST IN NATURE
A major category of materials is organic materials, compounds containing

carbon bonded to other elements (e.g., H, N, O, S, P and the halogens)
9
We encounter a huge number of
organic materials in our daily lives
• > 10 million organic compounds have been identified
• About 1000 new ones are discovered or synthesized and
identified each day
• Many of these compounds are of immense importance:

• Insecticides, pesticides, plant poisons • Vitamins, hormones
• Fuels • Synthetic pharmaceuticals, antibiotics
• Solvents • Foodstuffs, flavourings and preservatives
• Explosives • Apart from water, living things are largely
• Detergents made up of organic compounds, notably
• Wool, cotton, natural fibres proteins, fats, carbohydrates and nucleic
• Plastics, synthetic fibres, rubber acids.
POLYMERS 10
MSE 101 – APS 110 – MSE 219 – MSE 244 –
Intro to Eng Chem & Struct & Inorganic Mat
Materials Materials Charact of Chem &
Science Science Materials Processing
MSE 245 – Organic Materials Chemistry & Processing
MSE 398 – Materials MSE 316 –

MSE 355 – Materials
Manufacturing & Mechanical Behavior
Production
Design Laboratory of Materials
PEY
MSE 415 – Environmental MSE 401 – Materials Selection in

Degradation of Materials Design
FUTURE CAREER 11
You will learn basic principles behind
organic materials & processing
LEARNING A NEW FIELD IS LIKE LEARNING A NEW LANGUAGE

(OR A NEW SPORT, ARTISTIC PURSUIT, ETC.)
Need to start from the beginning (e.g., language)

- Learn the alphabet
- Use the alphabet to form words
- Understand what words mean & how to
pronounce them
- Recognize basic sentence structures
- Have a simple conversation
- Understand nuances in speaking/writing
- Deliver an impromptu speech/write original work
12
Organic Chemistry is the study of the chemical
& physical properties of compounds of carbon
Organic chemistry is a powerful tool that will allows you to
create new materials & better synthesize old ones
THIS COURSE AIMS TO FAMILIARIZE YOU WITH THE
FUNDAMENTALS OF THIS FIELD
• What are different types of organic molecules, what are
their properties, and why are they important in materials
science & engineering?
• What happens when you mix organic materials and how
can predict how they will react?
• How can organic chemistry be used to design new
materials (e.g., polymers) with specific properties that do
not exist in nature?
13
MSE 245 Course Outline
1. Review: bonding, Lewis structures, hybridization, acids base chemistry
2. Introduction to IUPAC nomenclature (handouts)
3. Alkanes and Cycloalkanes (Ch 3).
4. Alkenes and Alkynes (Ch 4).
5. Reactions of Alkenes. (Ch 5)
6. Chirality and the Handedness of Molecules (handouts)
7. Haloalkanes (Ch 7).
8. Alcohols, Ethers, and Thiols (Ch 8).
9. Benzene and its Derivatives (Ch 9).
10. Amines (Ch 10).
11. Aldehydes and Ketones (Ch13).
12. Carboxylic Acids and derivatives (Ch 14 &15)
13. Organic Polymer Chemistry and synthesis (Ch 16 + Brazel & Rosen Ch 1 & 2)
14. Polymer Physical properties (Brazel & Rosen Ch 3, 4, 5 and 6)
15. Polymer processing (Ch17 (Brazel & Rosen Ch-17)
16. Polymer recycling, degradation and environmental impact (handouts)
14
Review of Basic Concepts
• Carbon Atoms, Electrons and Orbitals

• Lewis Structures and Formal Charge
• Polar and nonpolar molecules
• Resonance
• Bonding and Hybridization
• Acid base chemistry
15
REVIEW
ATOMS, ELECTRONS & ORBITALS
16
Organic chemistry is essentially
the chemistry of carbon
• Most atoms are only capable of forming small molecules (a few
can form larger molecules). Carbon is, by far, the best atom for
making large molecules with.
• Carbon can make molecules that have tens, hundreds, thousands
even millions of atoms. The huge number of possible
combinations means that there are more Carbon compounds that
those of all the other elements put together.
• A single Carbon atom can combine with up to four other atoms.
We say it has a valency of 4. This means that Carbon atoms can
form chains and rings onto which other atoms can be attached.
This leads to a huge number of different compounds.
• Carbon compounds are classified according to how the carbon
atoms are arranged and what other groups of atoms are attached.
17
C is a small atom
Physical Properties
Atomic Number 6
Atomic Mass: 12.011
Melting Point: 3550°C
• It forms single, double, Boiling Point: 3825°C
and triple bonds. Density: 2.267g/cm3.
• It is intermediate in
electronegativity (2.5).
• It forms strong covalent
bonds with C, H, O, N, S,
the halogens, and some
metals.
Carbon has 6 electrons, 4 of the
Valence shell: Outermost electron electrons are in its valence shell
shell of an atom. (outer shell). The circles in the
Valence electrons: Electrons in the diagram show energy levels -
valence shell. representing increasing distances
https://www.sciencesfp.com/electronic-structure-of-matter.html
from the nucleus. 18
Recall: Electronic structure of atoms
• Shells are divided into subshells called orbitals, which
are designated by the letters s, p, d,…
• s (one per shell)
• p (set of three per shell 2 and higher)
• d (set of five per shell 3 and higher) …
19
Recall: Energy level diagrams
The pairing of
electron spins.
Rule 1: Orbitals fill in order of increasing energy from lowest to highest

Rule 2: Each orbital can hold up to 2 electrons with their spins paired. Spin
pairing means that each electron spins in direction opposite to its partner.
Rule 3: When orbitals of equivalent energy are available, but there are not
enough electrons to fill them completely, then we add one electron to each
equivalent orbital before we add a second electron to any one of them. 20
Energy level diagram of carbon
• Here we see carbon has 6
electrons represented by arrows
(the direction of the arrow
represents the electron spin)
• Two electrons are found in the 1s
orbital close to the nucleus.
• The next two will go into the 2s
orbital.
• The remaining ones will be in two
separate 2p orbitals.
• The actual location of electrons
cannot be determined with certainty
21
REVIEW
LEWIS STRUCTURES & FORMAL CHARGE
22
Recall: Lewis structures
• Valence shell: The outermost electron shell of an atom.
• Valence electrons: Electrons in the valence shell of an atom.
These electrons are used in forming chemical bonds.
• Lewis structure of an atom
• The symbol of the atom
represents the nucleus and all
inner shell electrons.
• Dots represent electrons in the
valence shell of the atom.
Hydrogen
Oxygen
Gilbert N. Lewis (1875-1946) Chlorine
Dean of Chemistry, University
of California, Berkeley Chloride ion 23
Lewis Model of Bonding
OCTET RULE
The tendency among atoms of Group 1A-7A elements to react in ways
that achieve an outer shell of 8 valence electrons.
• Atoms bond together so that each atom in the bond acquires the
electron configuration of the noble gas nearest it in atomic number.
• An atom that gains electrons becomes an anion.
• An atom that loses electrons becomes a cation.
• Ionic bond: A chemical bond resulting from the electrostatic attraction of
an anion and a cation.
• Covalent bond: A chemical bond resulting from two atoms sharing one or
more pairs of electrons.
• We classify chemical bonds as ionic, polar covalent, and nonpolar
covalent based on the difference in electronegativity between the
bonded atoms. 24
Lewis structures let us draw molecules
indicating bonds & unshared electron pairs
Hydrogen
Oxygen
25
Lewis Structure and Line-Bond (Kekule)
Structure
26
Recall: Valence-shell Electron-Pair Repulsion
(VSEPR) can predict molecular shapes
• Atoms are surrounded by regions of electron density.
• Regions of electron density repel each other.
27
Formal Charge is the charge on an
atom in a molecule or polyatomic ion
Formal charge is a way of counting electrons involved in bonding
• To determine Formal Charge
• Step 1: Write a Lewis structure for the molecule or ion.
• Step 2: Assign each atom all its unshared (nonbonding)
electrons and one-half its shared (bonding) electrons.
• Step 3: Compare this number with the number of
valence electrons in the neutral, unbonded atom.
• If the number is less than that assigned to the unbonded atom,
the atom has a positive formal charge.
• If the number is greater, the atom has a negative formal
charge.
28
Formal charge examples
For NO3-
29
Some additional points about
formal charge
1. The formal charge being a theoretical charge doesn’t
indicate any real charge separation in the molecule.
2. Formal charges help in the selection of the lowest
energy structure from a number of possible Lewis
structures for a given species.
3. Knowledge of the lowest energy structure helps in
predicting the major product of a reaction and also
describes a lot of phenomena.
4. Generally, the lowest energy structure is the one with
the smallest formal charges on the atoms and the most
distributed charge
30
Drawing Lewis structures
• Step 1: Determine the number of valence electrons in the
molecule or ion.
• Step 2: Write the skeleton structure (arrangement) of atoms.
• Step 3: Use 2 valence electrons to form each bond in the
skeleton structure (connect the atoms by single line between
atoms).
• Step 4: Try to satisfy the octet rule by distributing the remaining
electrons so that each atom has a complete valence shell. Use
multiple bonds when necessary to eliminate unpaired electrons.
• Show bonding electrons as single lines.
• Show nonbonding electrons as pairs of dots.
• Atoms share 1 pair of electrons in a single bond, 2 pairs in a double
bond, and 3 pairs in a triple bond.
• Step 5: Check for lowest formal charge possible for all the atoms
without violating the octet rule.
31
Example 1: Write the Lewis Structure of CO2
32
Some generalizations in neutral (uncharged)
organic compounds
• In neutral molecules containing C, H, N, O, and
halogen (X)
• H has one bond.
• C has 4 bonds and no unshared electrons.
• N has 3 bonds and 1 unshared pair of electrons.
• O has 2 bonds and 2 unshared pairs of electrons.
• X (i.e., F, Cl, Br and I) has 1 bond and 3 unshared pairs of
electrons.
33
REVIEW
POLAR & NONPOLAR MOLECULES
34
Electronegativity: A measure of the force of
an atom's attraction for the electrons it shares
in a chemical bond with another atom.
35
Electronegativity helps us to
predict the type of bonds formed
https://www.angelo.edu/faculty/kbo
udrea/periodic/physical_metals.htm 36
In polar covalent bonds, atoms
share electrons unequally
Nonpolar Bonds: covalent bond where atoms share electrons equally
• In a polar covalent bond:
• The more electronegative atom has a partial negative charge,
indicated by the symbol d–.
• The less electronegative atom has a partial positive charge,
indicated by the symbol d+.
• In an electron density model:
• Red indicates a region of
high electron density.
• Blue indicates a region of
low electron density.
37
Polar and Nonpolar Molecules
• A molecule with polar bonds is nonpolar if:
• The vector sum of its bonds dipoles is zero (that is, the
bond dipoles cancel each other).
• Carbon dioxide has two polar covalent bonds and
because of its geometry, is a nonpolar molecule.
38
• A water molecule has two polar covalent bonds
and, because of its geometry, is a polar molecule.
39
• An ammonia molecule has three polar covalent
bonds, and because of its geometry, is a polar
molecule.
40
• Chloromethane and formaldehyde are polar molecules.
• Acetylene is a nonpolar molecule.
41
REVIEW
RESONANCE
42
Sometimes molecules/ions cannot be
represented by a single Lewis structure
Lewis structures for the carbonate ion
The carbonate ion as a hybrid of three equivalent contributing

structures. Curved arrows show the redistribution of valence
electrons between one contributing structure and the next.
43
The curved arrow is a symbol used to show
redistribution of valence electrons
• In using curved arrows, there are only two allowed

types of electron redistribution:
• from a bond to an adjacent atom.
• from an atom to an adjacent bond.
• Electron pushing by the use of curved arrows is a
survival skill in organic chemistry.
• learn it well!
44
Resonance
• Many molecules and ions are best described by
writing two or more Lewis structures.
• Individual Lewis structures are called contributing
structures.
• Connect individual contributing structures by a
double-headed arrow.
• The molecule or ion is a hybrid of the various
contributing structures.
45
In resonance, all acceptable
contributing structures must:
1. Have the same number of valence electrons.
2. Obey the rules of covalent bonding.
• No more than 2 electrons in the valence shell of H.
• No more than 8 electrons in the valence shell of a 2nd period
element.
• 3rd period elements may have up to 12 electrons in their
valence shells.
3. Differ only in distribution of valence electrons.
4. Have the same total number of paired and unpaired
electrons.
46
REVIEW
BONDING & HYBRIDIZATION
47
Recall: Atomic orbitals have “shapes”
• All s orbitals have the shape of a
sphere, with its center at the
nucleus.
• Of the s orbitals, a 1s orbital is the
smallest, a 2s orbital is larger, and a 3s
orbital is larger still.
• A p orbital consists of two

lobes arranged in a straight
line with the center at the
nucleus.
• p orbitals come in sets of
three: 2px, 2py, and 2pz.
48
Orbital Overlap Model of Bonding
• A covalent bond forms when a portion of an atomic
orbital of one atom overlaps a portion of an atomic
orbital of another atom.
In forming the covalent bond in H–H, there is overlap of

the 1s orbitals of each hydrogen.
49
• Then, overlap of a 2s atomic orbitals of one atom
and 2p atomic orbitals of another atom would give
bond angles of approximately 90°.
• Instead, we observe bond angles of approximately
109.5°, 120°, and 180°.
• What actually happens is ‘hybridization’ of atomic
orbitals.
• 2nd row elements use sp3, sp2, and sp hybrid orbitals for
bonding.
50
• The atomic orbitals of different energies will mix to
form a new set of hybrid orbitals with energies
determined by a weighted average of the atomic
orbitals that combined.
• Hybrids are equivalent to one another in shape and
energy, differing only in their spatial orientation.
• The number of hybrid orbitals formed must equal the
initial number of atomic orbitals combined.
• Mixing one 2s orbital + one 2p orbital. The result must be
two sp hybrid orbitals.
• Mixing one 2s orbital + two 2p orbitals. The result must
be three sp2 hybrid orbitals.
• Mixing one 2s orbital + three 2p orbitals The result must
be four sp3 hybrid orbitals.
51
• Overlap of hybrid orbitals can form two types of covalent
bonds, depending on the geometry of the overlap:
• Sigma (s) bonds are formed by “direct” overlap.
• Pi (p) bonds are formed by “parallel” overlap.
(Ethylene) (Acetylene)
Single bond Double bond Triple bond

(s bond) (1 s bond & 1 p bond) (1 s bond & 2 p bonds)
Bond order = 1 Bond order = 2 Bond order = 3
s bonds are stronger than p bonds

↑ bond order, ↓ bond length
52
sp Hybrid Orbitals
A single sp hybrid orbital has two lobes of unequal size.
• The two sp hybrid orbitals lie in a line at an angle of 180°.
• The two unhybridized 2p orbitals are perpendicular to each
other and to the line through the two sp hybrid orbitals.
53
sp Hybridization
• In this case, hybrids are from mixing one s orbital + one p orbital. The bond angle
is 180 degrees.
• Since each sp hybrid has 50% s character and 50% p character, the hybrid orbital
energy lies halfway between that of the 2s orbital and the 2p orbital set.
• Notice that in an sp hybridized atom there are two unhybridized p orbitals in

addition to the two hybrids.
54
sp Hybridization
• Hybrid orbitals either serve as lone pair orbitals, or form sigma
bonds.
• The unhybridized p orbitals form pi bonds.
• Therefore, we would sp hybridize the carbon atoms in ethyne,
to account for the C-C triple bond (one sigma plus two pi bonds)
and the single C-H bonds (a sigma bond).
55
sp Hybrid Orbitals
Covalent bonding in ethyne. A carbon-carbon triple bond
consists of one sigma (s) bond and two pi (p) bonds.
56
sp2 Hybrid Orbitals
A single sp2 hybrid orbital has two lobes of unequal size:
• The three sp2 hybrid orbitals are directed toward the
corners of an equilateral triangle at angles of 120°.
• The unhybridized 2p orbital is perpendicular to the plane of
the three sp2 hybrid orbitals.
57
sp2 Hybridization
• Using 3 hybrids and 1 unhybridized p orbital, results in 3 equivalent hybrids
directed to the corners of an equilateral triangle, leaving 1 p orbital
perpendicular to the plane of the hybrids.
• A double bond is a sigma bond plus a pi bond, so these terminal carbon
atoms from three sigma and one pi bond.
• The sp2 hybrids has an equal bonding angle of 120 degree.
58
sp2 Hybrid Orbitals
Covalent bonding in ethene (ethylene). Ethene is a planar
molecule.
59
sp2 Hybrid Orbitals
A carbon-oxygen double bond consists of one sigma (s) bond and
one pi (p) bond.
60
sp3 Hybrid Orbitals
Each sp3 hybrid orbital has two lobes of unequal size.
• The four sp3 hybrid orbitals are directed toward the corners
of a regular tetrahedron at angles of 109.5°.
61
sp3 Hybridization
• A Lewis structure suggests that all the bonds were single, or sigma bonds and
we would need four equivalent hybrids.
• The structure is tetrahedral and all angles are 109.5 degree.
62
sp3 Hybrid Orbitals
Methane (CH4)
63
Ethane (C2H6)
64
sp3 Hybrid Orbitals
65
Summary of Carbon Hybridization
Number of Shape of
Hybrids Hybrids
Hybridization Types of Bonds to Carbon Example
(Groups Bonded (Predicted
to Carbon) Bond Angles)
Ethane
Tetrahedral 4 s bonds/lone pairs (4
sp3 4
(109.5∘) single bonds/lone pairs)
Ethene (ethylene)
3 s bonds/lone pairs + 1 p
Trigonal planar
sp2 3 bond (2 single bonds/lone
(120∘)
pairs + 1 double bond)
Ethyne (acetylene)
bonds (1 single bond/lone
sp 2 Linear (180∘)
pair + 1 triple bond or 2
double bonds)
66
REVIEW
ACID BASE CHEMISTRY
67
Recall: Brønsted-Lowry Acids & Bases
• Acid: A proton donor.
• Base: A proton acceptor.
• Conjugate base: The species formed from an acid
when an acid donates a proton to a base.
• Conjugate acid: The species formed from a base
when the base accepts a proton from an acid.
• Acid-base reaction: A proton-transfer reaction.
• Conjugate acid-base pair: Any pair of molecules or ions
that can be interconverted by transfer of a proton.
68
Brønsted-Lowry Acids & Bases
• Brønsted-Lowry definitions do not require water as
a reactant.
69
• We use curved arrows to show the flow of
electrons that occurs in the transfer of a proton
from acetic acid to ammonia.
70
Acid and Base Strength
• Strong acid: One that reacts completely or almost
completely with water to form H3O+ ions.
• Strong base: One that reacts completely or almost
completely with water to form OH– ions.
• Here are the six most common strong acids and the
four most common strong bases.
71
Acid and Base Strength
• Weak acid: A substance that only partially
dissociates in water to produce H3O+ ions.
• Acetic acid, for example, is a weak acid; in water, only 4
out every 1000 molecules are converted to acetate ions.
• Weak base: A substance that only partially

dissociates in water to produce OH– ions.
• ammonia, for example, is a weak base.
72
73
Recall: Acid-Base Equilibria
• To determine the position of equilibrium in an acid-
base reaction:
• Identify the two acids in the equilibrium; one on the left
and one on the right.
• Remember that the stronger acid gives the weaker
conjugate base, and the weaker acid gives the stronger
conjugate base.
• The stronger acid reacts with the stronger base to give
the weaker acid and weaker base.
• Equilibrium lies on the side of the weaker acid and the
weaker base.
74
pKa Values for Some Organic and
Inorganic Acids
75
Acid-Base Equilibrium
• Equilibrium in the following acid-base reaction lies
to the right, on the side of the weaker acid and the
weaker base.
76
Structure and Acidity
• The most important factor in determining the relative
acidity of an organic acid is the relative stability of the
anion, A–, formed when the acid, HA, transfers a
proton to a base.
• We consider these four factors:
1. The electronegativity of the atom bonded to H in HA.
2. Resonance stabilization of A–.
3. The inductive effect.
4. The size and delocalization of charge in A–.
• The more stable the anion A–, the greater the acidity of
the acid HA.
77
Structure and Acidity: Electronegativity
• Electronegativity of the atom bearing the negative
charge.
• Within a period
• The greater the electronegativity of the atom bearing the
negative charge, the more strongly its electrons are held.
• The more strongly electrons are held, the more stable the
anion A–.
• The more stable the anion A–, the greater the acidity of the
acid HA.
78
Structure and Acidity: Resonance
• Resonance delocalization of the charge on A–
• Compare the acidity of a carboxylic acid and an alcohol, both of which
contain an –OH group.
• Carboxylic acids are weak acids. Values of pKa for most unsubstituted
carboxylic acids fall within the range of 4 to 5.
• Alcohols are very weak acids. Values of pKa for most alcohols fall within the
range of 15 to 18.
• How do we account for the fact that carboxylic acids are stronger acids
than alcohols?
79
• The greater the resonance stabilization of the anion, the
more acidic the compound.
• There is no resonance stabilization in an alkoxide anion.
• We can write two equivalent contributing structures for
the carboxylate anion; the negative charge is spread
evenly over the two oxygen atoms.
80
Structure and Acidity: Inductive effect
• Inductive polarization of electron density
transmitted through covalent bonds caused by a
nearby atom of higher electronegativity
81
Structure and Acidity: Delocalization of
charge
• The more stable the anion A–, the greater the
acidity of the acid HA.
• The larger the volume over which the charge on an
anion (or cation) is delocalized, the greater the stability
of the anion (or cation).
• When considering the relative acidities of the hydrogen
halides, (HI > HBr > HCl > HF), we need to consider the
relative stabilities of the halide ions.
• Recall from general chemistry that atomic size is a
periodic property.
• For main group elements, atomic radii increase going
down a group and increase going across a period.
82
• For the halogens, iodine has the largest atomic radii,
fluorine has the smallest I > Br > Cl > F.
• Anions are always larger than the atoms from which they
are derived. For anions, nuclear charge is unchanged but
the added electron(s) introduce new repulsions and the
electron cloud swells.
• Among the halide ions, I– has the largest atomic radius,
and F– has the smallest atomic radius.
• Thus, HI is the strongest acid because the negative charge
on iodide ion is delocalized over a larger volume than the
negative charge on chloride, etc.
• The result of both resonance and the inductive effect is
due to the delocalization of charge.
83
Example
84
Lewis Acids and Bases
• Lewis acid: Any molecule or ion that can form a
new covalent bond by accepting a pair of
electrons.
• Lewis Base: Any molecule or ion that can form a
new covalent bond by donating a pair of electrons.
85
Lewis Acid: Electron pair acceptor
Lewis Base: Electron pair donor
Water Hydrogen chloride

(Lewis base) (Lewis acid)
• When HCl dissolves in water, for example, the strongest

available Lewis base is an H2O molecule, and the
following proton-transfer reaction takes place.
86
• When HCl dissolves in methanol, the strongest available

Lewis base is a CH3OH molecule, and the following
proton-transfer reaction takes place.
87
88
An important Lewis Acid: Carbocations
• Another type of Lewis acid we will encounter in
later chapters is an organic cation in which a
carbon is bonded to only three atoms and bears a
positive formal charge.
• such carbon cations are called carbocations
89
MSE245
Organic Materials
WB 138
January 17, 2024

3. Alkanes and Cycloalkanes (Ch 3).
4. Alkenes and Alkynes (Ch 4).
7. Haloalkanes (Ch 7).
8. Alcohols, Ethers, and Thiols (Ch 8).
9. Benzene and its Derivatives (Ch 9).
10. Amines (Ch 10).
11. Aldehydes and Ketones (Ch13).
2
1
Exercise: Can you name the following compounds?
CH3 CH 2 CH 3
CH3 CCH2 CHCH2 CH 3 4 6
1 3 5
CH3 2
4-Ethyl-2,2-dimethylhexane
Isopropylcyclopentane 1-tert-Butyl-4-methyl-
cyclohexane
3
1-Isobutyl-2-methyl- 1-Ethyl-1-methyl-
cyclohexane cyclopropane
Naming of Organic Compounds

IUPAC stands for the International Union of Pure and
Applied Chemistry.
This is an organization which regulates various

aspects of chemistry. It also issues rules for the
nomenclature (name-giving) of organic compounds.
2
What you need to learn
In this part:
• You need to be able to translate the name
of an organic compound into its structural
formula.
• You need to be able to name a compound
from its given formula.
Cracking the code
The IUPAC Nomenclature

• The increasingly large number of organic compounds
identified with each passing day, together with the fact that
many of these compounds are isomers of other compounds,
requires that a systematic nomenclature system be developed.
• Just as each distinct compound has a unique molecular
structure which can be designated by a structural formula,
each compound must be given a characteristic and unique
name.
• As organic chemistry grew and developed, many compounds
were given ‘common’ names, which are now commonly used
and recognized. Some examples are:
3
The two basic features of the IUPAC name
• Because every organic compound contains carbon, and almost
every one contains hydrogen, the names of these two elements
do not appear directly in the compound names.
• Instead, the IUPAC system names a compound based on the
number of carbon atoms linked together in the longest
continuous chain of carbon atoms, the first feature in forming
the IUPAC name.
• The second feature arises from the observation that different
organic compounds containing similar carbon or non-carbon
groups (so-called functional groups) within the molecules react
similarly. This leads to the compounds being grouped in families
according to the functional groups that they contain.
SOME BASICS
FUNCTIONAL GROUPS
4
There are 4 classes of hydrocarbons
Hydrocarbon: A compound that contains only carbon atoms and hydrogen atoms
Functional Groups
• Functional Group: An atom or group of atoms
within a molecule that shows a characteristic set of
physical and chemical properties.
• Functional groups are important for three reasons,
they are:
• The units by which we divide organic compounds into
classes.
• The sites of characteristic chemical reactions.
• The basis for naming organic compounds.
10
10
5
Functional Groups
• Alcohol: A compound that contains an –OH
(hydroxyl group) bonded to a tetrahedral carbon
atom.
11
11
Functional Groups
• Amine: A compound that contains an amino group:
a nitrogen atom bonded to one, two, or three
carbon atoms.
• Amines are classified as 1°, 2°, and 3° according to the
number of carbon atoms bonded directly to the nitrogen
atom.
12
12
6
Functional Groups
• Carbonyl group (C=O) of aldehydes and ketones.
13
13
Functional Groups
• Carboxyl group of carboxylic acids.
14
14
7
IUPAC NOMENCLATURE
BASICS
ALKANES
15
15
IUPAC- A General System

• prefix-infix(parent)-suffix
• prefix tells the number of carbon atoms in the parent
• infix tells the nature of the carbon-carbon bonds
• suffix tells the class of compound
Nature of Carbon-Carbon Suffix Class

Infix Bonds in the Parent Chain -e hydrocarbon
-an- all single bonds -ol alcohol
-en- one or more double bonds -al aldehyde
-yn- one or more triple bonds -amine amine
-one ketone
-oic acid carboxylic acid
16
16
8
IUPAC nomenclature for a straight chain
hydrocarbon with all single bonds (alkane)
• Suffix -ane specifies an alkane.
• Prefix tells the number of carbon atoms.
17
17
Names of Straight-Chain Alkanes
18
18
9
Alkane (CnH2n+2) with substituent (branched
group)
• Parent name: the longest carbon chain
• Substituent: a group bonded to the parent chain
• Alkyl group: a substituent derived by removal of a
hydrogen from an alkane; given the symbol R-
• CH4 becomes CH3- (methyl)
• CH3CH3 becomes CH3CH2- (ethyl)
19
19
Alkane with branched chains
20
20
10
IUPAC Nomenclature - Alkanes
1. The name of an alkane with an unbranched chain consists of a
prefix and the suffix -ane.
2. For branched alkanes, the parent chain is the longest chain of
carbon atoms.
3. Each substituent is given a name and a number.
4. If there is one substituent, number the chain from the end that
gives it the lower number.
21
21
IUPAC Nomenclature
5. If there are two or more identical substituents, number
the parent chain from the end that gives the lower
number to the substituent encountered first. The number
of times the substituent occurs is indicated by the prefixes
di-, tri-, tetra-, and so on.
22
22
11
IUPAC Nomenclature
6. If there are two or more different substituents,
• list them in alphabetical order.
• number from the end of the chain that gives the
substituent encountered first the lower number.
23
23
IUPAC Nomenclature
7. The prefixes di-, tri-, tetra-, etc. are not included
in alphabetization. Iso, as in isopropyl, is included
in alphabetization. In the following example, the
alphabetizing names are ethyl and methyl.
24
24
12
Some Alkyl Groups
25
25
Classification of Carbons
• Primary (1°): a C bonded to one other carbon
• Secondary (2°): a C bonded to two other carbons
• Tertiary (3°): a C bonded to three other carbons
• Quaternary (4°): a C bonded to four other carbons
26
26
13
Example: Draw the Structure
• Write the structural formula for 2,3-dimethylbutane.
• Write the structural formula for 3-ethyl-2-methylhexane.
27
27
IUPAC NOMENCLATURE
BASICS
CYCLOALKANES
28
28
14
Cycloalkanes (CnH2n)
In a cycloalkane, the carbon atoms are joined up in a ring - hence
cyclo.
1. Find the parent
1. If the ring contains equal or more carbons – cycloalkane (five- and six-
membered rings are the most common)
2. If the chain is longer, the parent is alkane and ring is a substituent
2. Number the ring
1. #1 is the first substituent in alphabetical order
2. Number the rest to make the substituent the lowest possible
3. If only one substituent, leave out the number
4. If two substituents, number from the substituent of lower alphabetical order
5. If three or more substituents, number to give them the lowest set of
numbers, and then list substituents in alphabetical order
29
29
Cycloalkanes
• Commonly written as line-angle formulas
• Examples:
Isopropylcyclopentane
1-tert-Butyl-4-methyl-
cyclohexane
cyclohexane
cyclohexane
cyclohexane
1-Isobutyl-2-methyl-
1-Isobutyl-2-methyl- 1-Ethyl-1-methyl-
1-Ethyl-1-methyl-
1-Ethyl-1-methyl-
cyclohexane
cyclohexane 1-Ethyl-1-methyl-
cyclopropane
cyclopropane
cyclohexane
cyclohexane cyclopropane
cyclopropane
30
30
15
IUPAC NOMENCLATURE
BASICS
ALKENES/CYCLOALKENES, AKLYNES/CYCLOALKENES, ARENES
31
31
Recall: Unsaturated Hydrocarbons

• Unsaturated Hydrocarbon: A hydrocarbon that
contains one or more carbon-carbon double or
triple bonds or benzene-like rings.
• Alkene: contains a carbon-carbon double bond and has
the general formula CnH2n.
• Alkyne: contains a carbon-carbon triple bond and has
the general formula CnH2n-2.
32
32
16
Unsaturated Hydrocarbons
• Arene: benzene and its derivatives (Ch 9)
33
33
Benzene and Phenyl Groups

• We do not study benzene and its derivatives until
Chapter 9, we show structural formulas of
compounds containing a phenyl group before that
time.
• The phenyl group is not reactive under any of the
conditions we describe in chapters 5-8.
34
34
17
IUPAC Rules for Alkenes
1. The –ene suffix (ending) indicates an alkene or cycloalkene.
2. The longest chain chosen for the root name must include both carbon atoms
of the double bond.
3. The root chain must be numbered from the end nearest a double bond
carbon atom. If the double bond is in the center of the chain, the nearest
substituent rule is used to determine the end where numbering starts.
4. The smaller of the two numbers designating the carbon atoms of the double
bond is used as the double bond locator. If more than one double bond is
present the compound is named as a diene, triene or equivalent prefix
indicating the number of double bonds, and each double bond is assigned a
locator number.
35
35
IUPAC Names for Alkenes (CnH2n)

• The –ene name is given to
the C=C double bond
function.
• The double bond may
appear anywhere in the
chain of carbons and so
requires a position
identifier (this is similar to
the –yne function).
• Study the following simple
examples of the alkene
family, given with their
names and models
36
36
18
Common Names of Some
Alkenes vs. IUPAC names
• Some alkenes, particularly low-molecular-weight
alkenes, are known almost exclusively by their
common names.
37
37
38
38
19
Example: Try on your own
• Write the structural formula for but-1-ene or 1- butene
• Number and name the following:
39
39
IUPAC Names for Cycloalkenes

1. In cycloalkenes, the double bond carbons are assigned ring locations
#1 and #2. Which of the two is #1 may be determined by the nearest
substituent rule.
2. Substituent groups containing double bonds are:
H2C=CH– Vinyl group
H2C=CH–CH2– Allyl group
4 2
1 CH 3
5
3 CH 3 3
4
1 2
6 CH 3
5
3-Methylcyclo- 1,6-Dimethylcyclo-
pentene hexene
40
40
20
Nomenclature of Alkynes (CnH2n-2)
• IUPAC nomenclature of alkynes
• Use the infix + suffix -yne to show the presence of a
carbon-carbon triple bond.
• Number the parent chain to give the first carbon of the
triple bond the lower number.
• Follow IUPAC rules for numbering and naming
substituents.
41
41
Alkynes (CnH2n-2)
• Functional group suffix = -yne . Rules are similar to –ene .
• Like the –ene function, the double bond may appear
anywhere in the chain of carbons and so requires a position
identifier.
• Disubstituted alkynes, R-C≡C-R', are described as "internal" alkynes
• Monosubstituted alkynes, R-C≡C-H, are described as "terminal"
alkynes.
42
42
21
IUPAC NOMENCLATURE
BASICS
HALOALKANES (ALKYL HALIDES)
43
43
Structure
• Haloalkane (alkyl halide): A compound containing a
halogen atom covalently bonded to an sp3 hybridized
carbon.
• given the symbol RX
• Halogens: F, Cl, Br; I
44
44
22
Nomenclature - IUPAC
• Locate the parent alkane.
• Number the parent chain to give the substituent encountered first the
lower number.
• Show halogen substituents by the prefixes fluoro-, chloro-, bromo-, and
iodo- and list them in alphabetical order with other substituents.
• Locate each halogen on the parent chain.
45
45
Nomenclature
• Several polyhaloalkanes are common solvents and
are generally referred to by their common or trivial
names.
46
46
23
IUPAC NOMENCLATURE
BASICS
ALCOHOLS, ALDEHYDES, KETONES, CARBOXYLIC ACIDS,
AMINES
47
47
Alcohols – IUPAC Nomenclature

• The parent chain is the longest chain that contains
the -OH group.
• Number the parent chain in the direction that gives
the -OH group the lower number.
• Change the suffix -e to -ol.
• Common names
• Name the alkyl group bonded to oxygen followed by the
word alcohol.
48
48
24
Alcohols - Nomenclature
• Examples:
49
49
Alcohols
• Functional class name = alkyl alcohol e.g. ethyl alcohol
• Substituent suffix = -ol e.g. ethanol
• Substituent prefix = hydroxy- e.g. hydroxyethane
• Structural unit: alcohols contain R-OH
50
50
25
• Compounds containing
• two -OH groups are named as diols,
• three -OH groups are named as triols.
• Compounds containing two -OH groups on are called
glycols.
51
51
• Unsaturated alcohols
• The double bond is shown by the infix -en-.
• The hydroxyl group is shown by the suffix -ol.
• Number the chain to give OH the lower number.
52
52
26
IUPAC NOMENCLATURE
BASICS
SUMMARY
53
53

• prefix-infix-suffix
• Prefix tells the number of carbon atoms in the parent.
• Infix tells the nature of the carbon-carbon bonds.
• Suffix tells the class of compound.
54
54
27
• prefix-infix-suffix
• Prefix tells the number of carbon atoms in the parent.
• Infix tells the nature of the carbon-carbon bonds.
• Suffix tells the class of compound.
55
55
IUPAC - a general system

prop-en-e = propene
eth-an-ol = ethanol
but-an-one = butanone
but-an-al = butanal
pent-an-oic acid = pentanoic acid
cyclohex-an-ol = cyclohexanol
eth-yn-e = ethyne
eth-an-amine = ethanamine
56
56
28
Functional Group of Organic Compounds
57
57
58
58
29
59
59
30
MSE245
Organic Materials
WB 138
January 24, 2024

3. Alkanes and Cycloalkanes (Ch 3)
4. Alkenes and Alkynes (Ch 4)
7. Haloalkanes (Ch 7)
8. Alcohols, Ethers, and Thiols (Ch 8)
9. Benzene and its Derivatives (Ch 9)
10. Amines (Ch 10)
11. Aldehydes and Ketones (Ch13)
2
1
Alkanes and Cycloalkanes
• Introduction & structure (3.1, nomenclature - 3.3,
IUPAC -3.5)
• Constitutional isomerism in alkanes (3.2)
• Cycloalkanes (3.4)
• Conformational isomers in alkanes and
cycloalkanes (3.6)
• Cis-trans isomerism in cycloalkanes (3.7)
• Physical properties of alkanes and cycloalkanes
(3.8)
• Reactions of alkanes (3.9)
• Sources of alkanes (3.10)
ALKANES &
CYCLOALKANES
INTRODUCTION & STRUCTURE
2
Hydrocarbon: A compound composed only of carbon and hydrogen
Saturated hydrocarbon:
A hydrocarbon containing
only carbon-carbon single
bonds.
Alkane : A saturated
hydrocarbon whose
carbons are arranged
in an open chain.
• Hydrocarbons which do not contain a benzene ring are called

aliphatic hydrocarbons. Those which do contain benzene are
called aromatic hydrocarbons.
3
Structure of Alkanes
• Shape
• Tetrahedral geometry (all carbons are sp3 hybridized).
• All bond angles are approximately 109.5°.
Recall (from Week 1)
Pentane (C5H12)
Alkanes have the general formula CnH2n+2
4
Representing Alkanes
• Line-angle formula: an abbreviated way to draw
structural formulas.
• Each line represents a single bond.
• Each line ending represents a CH3 group.
• Each vertex (angle) represents a carbon atom.
ALKANES &
CYCLOALKANES
CONSTITUTIONAL ISOMERISM IN ALKANES
10
10
5
Constitutional Isomers
• Constitutional (structural) isomers: Compounds
with the same molecular formula but a different
connectivity of their atoms.
• There are two constitutional isomers with the molecular
formula C4H10.
11
11
Example
• Draw and name all of the constitutional (structural) isomers of C6H14.
12
12
6
Constitutional Isomerism
• The potential for constitutional isomerism from just the
elements C and H is enormous
Molecular Constitutional
Fo rmula Isomers
CH 4 01 World population
C 5 H1 2 3 is about
>8,000,000,000
C 1 0 H2 2 75
C 1 5 H3 2 4,347
C 2 5 H5 2 36,797,588
C 3 0 H6 2 4,111,846,763
13
13
ALKANES &
CYCLOALKANES
CYCLOALKANES
14
14
7
Recall (last week): Naming cycloalkanes (CnH2n)
In a cycloalkane, the carbon atoms are joined up in a ring - hence
cyclo.
1. Find the parent
1. If the ring contains equal or more carbons – cycloalkane (five- and six-
membered rings are the most common)
2. If the chain is longer, the parent is alkane and ring is a substituent
2. Number the ring
1. #1 is the first substituent in alphabetical order
2. Number the rest to make the substituent the lowest possible
3. If only one substituent, leave out the number
4. If two substituents, number from the substituent of lower alphabetical order
5. If three or more substituents, number to give them the lowest set of
numbers, and then list substituents in alphabetical order
Methylcyclopentane
15
15
Name of Cycloalkanes
16
16
8
Cycloalkanes
• Cycloalkanes have two less hydrogen atoms than the parent alkane
and a generic formula of CnH2n.
• Cycloalkanes with a single ring are named analogously to their
normal alkane counterpart of the same carbon count:
cyclopropane, cyclobutane, cyclopentane, cyclohexane, etc.
• Cycloalkanes are classified into small, normal and bigger
cycloalkanes, where cyclopropane and cyclobutane are the small
ones, cyclopentane, cyclohexane, cycloheptane are the normal
ones, and the rest are the bigger ones.
• The larger cycloalkanes, with greater than 20 carbon atoms are
typically called cycloparaffins.
• The normal and the bigger cycloalkanes are very stable, like
alkanes, and their reactions, for example, radical chain reactions,
are like alkanes
17
17
ALKANES &
CYCLOALKANES
CONFORMATIONAL ISOMERS IN ALKANES
18
18
9
Recall from Week 1: A covalent bond forms when a portion of
an atomic orbital of one atom overlaps a portion of an atomic
orbital of another atom.
Ethane (C2H6)
19
19
Conformation (Linear)
• Conformation: Any three-dimensional arrangement
of atoms in a molecule that results from rotation
about a single bond.
• Staggered conformation: A conformation about a
carbon-carbon single bond where the atoms on one
carbon are as far apart as possible from the atoms on an
adjacent carbon. On the right is a Newman projection
formula.
20
20
10
Conformation
• Eclipsed conformation: A conformation about a
carbon-carbon single bond in which the atoms on one
carbon are as close as possible to the atoms on an
adjacent carbon.
• The lowest energy (most stable) conformation of an

alkane is a fully staggered conformation.
21
21
Conformation
• Torsional strain: Strain that arises when
nonbonded atoms separated by three bonds are
forced from a staggered conformation to an
eclipsed conformation.
• Also called eclipsed interaction strain.
• The torsional strain between staggered and eclipsed
ethane is approximately 12.6 kJ/mol (3.0 kcal/mol).
22
22
11
Example: (2,3-dimethylbutane) from C2-C3
Butane
23
23
Structure of Cycloalkanes
• The smallest alkane that can form a ring is cyclopropane,
C3H6. The angle between adjacent C-C bonds is only 60º (<<
109.5 angle in a tetrahedron). Cyclopropane is therefore
susceptible to chemical reactions that can open up the three-
membered ring.
• Any 4 carbons that form a cyclobutane ring into a plane of
atoms produces a structure where the angle between
adjacent C-C bonds is 90º.
24
24
12
Cyclopentane conformation
• In planar cyclopentane, all C-C-C bond angles are 108°,
which differ only slightly from the ideal tetrahedral
angle of 109.5°.
• Consequently there is little angle strain.
• Angle strain: Strain that arises when a bond angle is
either compressed or expanded compared with its
optimal value.
• Cyclopentane is not a planar molecule, because
displacing two of the carbon atoms from the plane of
the other three produces a puckered structure that
relieves some of the repulsion between the hydrogen
atoms on adjacent carbon atoms in the ring.
25
Cyclopentane conformation
• In planar cyclopentane, there are 10 fully eclipsed C-H
bonds creating a torsional strain of approximately 42
kJ/mol (10 kcal/mol).
• Puckering to an “envelope” conformation relieves part
of this strain
• In an envelope conformation, eclipsed interactions are
reduced but angle strain is increased slightly (105°).
26
13
Cyclohexane conformation
• Chair cyclohexane: Six C–H bonds are equatorial and
six are axial.
• An equatorial bond extends from the ring roughly

perpendicular to the imaginary axis of the ring.
• An axial bond extends from the ring roughly parallel to
the imaginary axis of the ring.
27
Cyclohexane conformation
• Boat conformation: A puckered conformation in which carbons 1 &
4 are bent toward each other.
• A boat conformation is less stable than a chair conformation by
27 kJ/mol (6.5 kcal/mol).
• Torsional strain is created by four sets of eclipsed hydrogen
interactions.
• Steric strain (nonbonded interaction strain) is created by one
set of flagpole interactions.
28
14
Chair cyclohexane
• There are two equivalent chair conformations.
• The alternative chair conformation interconvert via a
boat conformation.
• All C–H bonds that are equatorial in one chair are
axial in the alternative chair, and vice versa.
29
Methylcyclohexane
• A group equatorial in one chair is axial in the alternative
chair.
• The two chairs are no longer of equal stability. They
differ by 7.28 kJ/mol (1.74 kcal/mol)
30
15
ALKANES &
CYCLOALKANES
CIS-TRANS ISOMERISM IN CYCLOALKANES
31
31
Cis-trans Isomers
• Have the same molecular formula.
• Have the same connectivity of their atoms.
• Have an arrangement of atoms in space that cannot be interconverted
by rotation about sigma bonds.
A cyclopentane ring is commonly viewed through an edge or from above.
32
32
16
Cis-trans isomerism
A cyclohexane ring is commonly viewed as a planar
hexagon viewed from the side or from above.
33
33
Example: Cis-trans isomerism

• Which cycloalkanes show cis-trans
isomerism?
• Methylcyclopentane
• 1,1-Dimethylcyclobutane
• 1,3-Dimethylcyclobutane
34
34
17
Cis-trans isomerism
• Or we can represent a cyclohexane as a chair
conformation.
• In viewing chair conformations, groups equatorial in one
chair are axial in the alternative chair.
• For trans-1,4-dimethylcyclohexane, the diequatorial
chair is more stable than the diaxial chair.
35
Cis-trans isomerism
• For cis-1,4-dimethylcyclohexane, the alternative chairs
are of equal stability.
36
18
ALKANES &
CYCLOALKANES
PHYSICAL PROPERTIES
37
37
Physical Properties
• Alkanes are nonpolar compounds and have only
weak interactions between their molecules
• Dispersion forces: very weak intermolecular forces
of attraction resulting from interaction of
temporary induced dipoles
38
38
19
Physical Properties
• Boiling point
• Low-molecular-weight alkanes (1 to 4 carbons) are gases
at room temperature; e.g., methane, propane, butane.
• Higher-molecular-weight alkanes (5 to 17 carbons) are
liquids at room temperature (e.g., hexane, decane, gasoline,
kerosene).
• High-molecular-weight alkanes (18 or more carbons) are
white, waxy semisolids or solids at room temperature (e.g.,
paraffin wax).
• Density
• Average density is about 0.7 g/mL, higher MW alkanes is
~0.8 g/mL.
• Liquid and solid alkanes float on water (1.0 g/mL).
39
39
Boiling point and Melting point
40
40
20
Physical Properties
• Constitutional isomers are different compounds
and have different physical properties.
41
41
Physical Properties of Alkanes

Boiling point decreases as chain becomes more branched
• Long, straight chains

• Higher boiling point • Branched chains
• More surface area for dispersion forces • More spherical
42
42
21
Solubility of alkanes
• Alkanes are insoluble in water because the polar water
molecules are not attracted to the non-polar alkane
molecules.
• Alkanes are soluble in non-polar solvents such as
Carbon Tetrachloride, CCl4.
• Generally, “like dissolves in like and unlike do not
dissolve”. So non-polar substances will be insoluble in
polar solvents such as water, but they will be soluble in
non-polar solvents (like dissolves in like).
43
43
Properties of Cycloalkane
• Differences reflect subtle structural variations, including the greater bond energy of 1°
C–H versus 2° C–H bonds and steric crowding of neighboring groups.
• In small-ring cyclic compounds, ring strain (angle strain & torsional strain) can be a
major contributor to thermodynamic stability and chemical reactivity. Angle strain
results when a bond angle is expanded/compressed compared with optimal values.
• Very similar reactivity to the closely related alkanes. Both the C-H and C-C bonds are
non-polar. Cycloalkanes, like alkanes, are not very reactive.
Cycloalkane CH2 Units ΔH25º ΔH25º Ring Strain
(CH2)n n kcal/mole per CH2 Unit kcal/mole
Cyclopropane n=3 468.7 156.2 27.6
Cyclobutane n=4 614.3 153.6 26.4
Cyclopentane n=5 741.5 148.3 6.5
Cyclohexane n=6 882.1 147.0 0.0
Cycloheptane n=7 1035.4 147.9 6.3
Cyclooctane n=8 1186.0 148.2 9.6
Cyclononane n=9 1335.0 148.3 11.7
Cyclodecane n = 10 1481 148.1 11.0
44
CH3(CH2)mCH3 m = large — 147.0 0.0
44
22
ALKANES &
CYCLOALKANES
REACTIONS
45
45
Reactions of Alkanes
The alkanes and cycloalkanes, with the exception of cyclopropane, are probably
the least chemically reactive class of organic compounds.
Despite their relative inertness, alkanes undergo several important reactions:
1. Combustion
The combustion of carbon compounds, especially hydrocarbons, has been the
most important source of heat energy for human civilizations throughout
recorded history. However, the massive and uncontrolled chemical changes
that take place in combustion make it difficult to deduce mechanistic paths.
2. Halogenation
Halogenation is the replacement of one or more hydrogen atoms in an organic
compound by a halogen (fluorine, chlorine, bromine or iodine). Unlike the
complex transformations of combustion, the halogenation of an alkane appears
to be a simple substitution reaction.
3. Pyrolosis (Cracking)
The alkanes break down to smaller molecules in the absence of oxygen.
46
46
23
Alkane Combustion
• Oxidation is the basis for the use of alkanes as
energy sources for heat and power.
• Heat of combustion: the heat released when one mole
of a substance is oxidized to carbon dioxide and water.
47
47
Alkane Combustion
• In the absence of a spark or a high-intensity light source, alkanes
are generally inert to chemical reactions.
• However, alkanes burst into flame in the presence of a spark.
Once the reaction is ignited by a spark, these hydrocarbons burn
to form CO2 and H2O and give off between 45 and 50 kJ of energy
per gram of fuel consumed.
CH4(g) + 2 O2(g)® CO2(g) + 2 H2O(g)
the mixture of butane and isobutane used in disposable cigarette
lighters,
2 C4H10(g) + 13 O2(g) ® 8 CO2(g) + 10 H2O(g)
the mixture of C5 to C6 hydrocarbons in charcoal lighter fluid,
C5H12(g) + 8 O2(g) ® 5 CO2(g) + 6 H2O(g)
or the complex mixture of C6 to C8 hydrocarbons in gasoline.
2 C8H18(l) + 25 O2(g) ® 16 CO2(g) + 18 H2O(g)
48
48
24
49
49
Example: Burning of Long chain Carbon (Fat)

• The burning fat converts the water (being poured on it) to steam
• Steam takes up many more times the room of liquid water – one litre
of water converts to 1,700 litres of steam. Evaporating so quickly, the
rising steam takes with it fat molecules which instantly catch fire.
The result can be severe burns and even death.
• Any burning fat in your kitchen should never be extinguished with
water.
• What should you use in case of such type of fire?
50
50
25
Halogenation
In the presence of light, or at high temperatures, alkanes react with halogens to form
haloalkanes (alkyl halides). It is a type of substitution reaction.
Reaction with chlorine gives an alkyl chloride.
CH4(g) + Cl2(g)(light) ® CH3Cl(g) + HCl(g)
Reaction with bromine gives an alkyl bromide.
CH4(g) + Br2(l)(light)® CH3Br(g) + HBr(g)
1. The reactivity of the halogens decreases in the following order: F2 > Cl2 > Br2 >I2.
2. Since fluorine is so explosively reactive it is difficult to control, and iodine is
generally un-reactive, chlorine and bromine are more common.
3. Chlorinations and brominations are normally exothermic.
4. Energy input in the form of heat or light is necessary to initiate these halogenations.
5. Halogenation reactions may be conducted in either the gaseous or liquid phase.
• In gas phase chlorinations, the presence of oxygen (a radical trap) inhibits the
reaction.
• In liquid phase halogenations, radical initiators such as peroxides facilitate the
reaction. 51
51
Cracking is a process whereby a larger saturated

hydrocarbon is broken down into smaller hydrocarbons
Saturated hydrocarbon can be converted into an unsaturated hydrocarbon plus H2
52
52
26
ALKANES &
CYCLOALKANES
SOURCES
53
53
Sources of Alkanes
• Natural gas
• 90-95% methane, 5-10% ethane
• Petroleum
• gases (bp below 20°C)
• naphthas, including gasoline (bp 20 - 200°C)
• kerosene (bp 175 - 275°C)
• fuel oil (bp 250 - 400°C)
• lubricating oils (bp above 350°C)
• asphalt (residue after distillation)
• Coal
54
54
27
Synthesis Gas (Syngas)
• a mixture of carbon monoxide and hydrogen in varying
proportions, depending on how it is produced
C + H2O heat CO + H2
Coal
catalyst
CH4 + 1 O2 CO + 2H2
2
Methane
• methanol and acetic acid are produced from synthesis gas
catalyst
CO + 2H2 CH 3OH
Methanol
O
catalyst
CH 3 OH + CO CH 3 COH
Methanol Acetic acid 55
55
Petroleum and Natural Gas

• The term petroleum comes from the Latin stems petra, "rock,"
and oleum, "oil." It is used to describe a broad range of
hydrocarbons that are found as gases, liquids, or solids beneath
the surface of the earth. The two most common forms are
natural gas and crude oil.
• Natural gas is a mixture of lightweight alkanes. A typical sample
of natural gas when it is collected at its source contains 80%
methane (CH4), 7% ethane (C2H6), 6% propane (C3H8), 4%
butane and isobutane (C4H10), and 3% pentanes (C5H12). The C3,
C4, and C5 hydrocarbons are removed before the gas is sold. The
commercial natural gas delivered to the customer is therefore
primarily a mixture of methane and ethane. The propane and
butanes removed from natural gas are usually liquefied under
pressure and sold as liquefied petroleum gases (LPG).
56
56
28
Crude Oil - Petroleum Fractions
• Crude oil is a complex mixture that is between 50 and 95% hydrocarbon
by weight.
• The first step in refining crude oil involves separating the oil into different
hydrocarbon fractions by distillation. Since there are a number of factors
that influence the boiling point of a hydrocarbon, these petroleum
fractions are complex mixtures.
Fraction Boiling Range (oC) Number of Carbon Atoms
natural gas < 20 C1 to C4
petroleum ether 20 - 60 C5 to C6
gasoline 40 - 200 C5 to C12, mostly C6 to C8
kerosene 150 - 260 mostly C12 to C13
fuel oils > 260 C14 and higher
lubricants > 400 C20 and above
asphalt or coke residue polycyclic
57
57
Crude Oil Distillation

Natural gas (C1-C4)
Straight run gasoline (C5-C10) (Tbp: 30-

200 oC)
Kerosene (lamp oil) (C11-C14) (Tbp:

175-300 oC)
Heating Oil, Diesel fuel (C14-C25) (Tbp:

275-400 oC)
Lubricating oils, waxes (distilled under

reduced pressure)
Asphalt (undistillable tarry residue)
Before the automobile, kerosene used

for lamp oil was the most desired
product and gasoline which was
too volatile, was considered a
waste product. 58
58
29
https://www.youtube.com/watch?v=jk0WrtA8_T8 59
59
30
MSE245
Organic Materials
WB 138
January 24, 2024

10. Amines (Ch 10)
2
1
Alkenes and Alkynes
• Introduction & structure (4.1)

• Nomenclature (focusing on isomers) (4.2)
• Physical properties (4.3)
• Acidity of 1-alkynes (4.4)
ALKENES & ALKYNES

INTRODUCTION
2
Hydrocarbon: A compound composed only
Unsaturated hydrocarbon: A
of carbon and hydrogen
hydrocarbon that contains one or
more carbon-carbon double or
Alkene : contains a
carbon-carbon
double bond and has
the general formula
CnH2n.
Alkyne : contains a
carbon-carbon triple
bond and has the
general formula
CnH2n-2.
We do not study arenes (benzene and its

derivatives) until Chapter 9
• However, we show structural formulas of compounds containing a phenyl

group before that time.
• The phenyl group is not reactive under any of the conditions we describe in
chapters 5-8.
3
ALKENES & ALKYNES
ALKENE STRUCTURE
Recall (Week 1): Bonding & hybridization

• Mixing one 2s orbital + one 2p orbital. The result must
be two sp hybrid orbitals.
8
4


9
Recall (Week 1): Summary of Carbon

Hybridization
Number of Shape of
Hybrids Hybrids
Hybridization Types of Bonds to Carbon Example
(Groups Bonded (Predicted
to Carbon) Bond Angles)
Ethane
Tetrahedral 4 s bonds/lone pairs (4
sp3 4
(109.5∘) single bonds/lone pairs)
Ethene (ethylene)
Trigonal planar 3 s bonds/lone pairs + 1 p
sp2 3 bond (2 single bonds/lone
(120∘)
pairs + 1 double bond)
Ethyne (acetylene)
bonds (1 single bond/lone
sp 2 Linear (180∘)
pair + 1 triple bond or 2
double bonds)
10
10
5
Structure of Alkenes
• The alkene functional group consists of two sp2 hybridized C atoms
bonded to each other via a σ and a π bond.
• In ethene (ethylene; C2H4), four other σ bonds between the sp2

hybridised C and H 1s make 4 C-H bonds to complete the σ bond
framework.
• The π bond is produced by the side-to-side overlap of the p-orbitals not
utilized in the hybrids.
• The 2 C of the C=C and the 4 H atoms attached directly to the C=C are
all in the same plane, with bond angles ~120°.
11
11
Structure of Alkenes
• According to the orbital overlap model, a double bond
consists of:
• one s bond formed by overlap of sp2 hybrid orbitals, and
• one p bond formed by overlap of parallel 2p orbitals.
• Rotating by 90° breaks the pi bond
12
6
Structure of Alkynes
• The functional group of an alkyne is a carbon-carbon
triple bond.
• A triple bond consists of:
• One s bond formed by the overlap of sp hybrid orbitals.
• Two p bonds formed by the overlap of sets of parallel 2p
orbitals.
13
ALKENES & ALKYNES

NOMENCLATURE (FOCUSING ON ISOMERS)
14
14
7
Recall (last week): IUPAC Rules for Alkenes
1. The –ene suffix (ending) indicates an alkene or cycloalkene.
2. The longest chain chosen for the root name must include both carbon atoms
of the double bond.
3. The root chain must be numbered from the end nearest a double bond
carbon atom. If the double bond is in the center of the chain, the nearest
substituent rule is used to determine the end where numbering starts.
4. The smaller of the two numbers designating the carbon atoms of the double
bond is used as the double bond locator. If more than one double bond is
present the compound is named as a diene, triene or equivalent prefix
indicating the number of double bonds, and each double bond is assigned a
locator number.
15
15
Recall (last week): Common Names of

Some Alkenes vs. IUPAC names
• Some alkenes, particularly low-molecular-weight
alkenes, are known almost exclusively by their
common names.
16
16
8
Recall (last week): Alkynes (CnH2n-2)
identifier.
alkynes.
17
17
Recall (last class): Cis-trans Isomers

• Have the same molecular formula.
• Have the same connectivity of their atoms.
• Have an arrangement of atoms in space that cannot be interconverted
by rotation about sigma bonds.
A cyclopentane ring is commonly viewed through an edge or from above.
18
18
9
Cis-Trans Isomerism
• Because of restricted rotation about a C–C double
bond, groups on the carbons of a double bond are
either cis or trans to each other.
• Because of nonbonded interaction strain between alkyl
substituents on the same side of the double bond, a
trans alkene is more stable than an isomeric cis alkene.
19
Isomers in Alkenes
Are these cis-trans isomers?
20
20
10
Configuration: Cis-Trans
• The cis-trans system: Configuration is determined
by the orientation of atoms of the main chain.
21
21
Cis-Trans Isomerism
• The configuration of the double bond in cyclopropene
through cycloheptene must be cis. These rings are not
large enough to accommodate a trans double bond.
• Cyclooctene is the smallest cycloalkene that can
accommodate a trans double bond.
22
11
Rearrangement reactions
• It occurs when a single reactant undergoes a
reorganization of bonds and atoms to yield a single
isomeric product.
23
23
Cis-Trans Isomerism
• Dienes, trienes, and polyenes
• For an alkene with n carbon-carbon double bonds, each
of which can show cis-trans isomerism, 2n cis-trans
isomers are possible.
• Consider 2,4-heptadiene; it has four cis-trans isomers,
two of which are drawn here.
24
12
Cis-Trans Isomerism
• Vitamin A has five C-C double bonds, four of which can
show cis-trans isomerism.
• Vitamin A is the all-trans isomer.
cis-trans system: names geometric/conformational isomers

(where the same groups are arranged differently on an alkene)
25
E,Z designation specifies the configuration of

groups on highly substituted alkenes
• The E- and Z- style is more reliable and particularly suited to highly
substituted alkenes, especially when the substituents are not alkyl
groups.
• These rules are based on atomic number, and the first point of difference.
Imagine each alkene as two pieces, each piece containing one of the sp2
carbons
• Assign the priority (high = 1, low = 2) to each group on each sp2 C based on
atomic number
• Determine the relative position of the two higher priority groups
• If they are on the same side then it is a (Z)-alkene (German; zusammen =
together)
• If they are on opposite sides then it is an (E)-alkene (German; entgegen =
opposite)
• If there is more than one C=C that can be E/Z, then the location needs to be
included with the locant, e.g. (2E,4Z)
26
26
13
Configuration: E,Z
• To assign an E,Z configuration, first assign a priority
to the substituents on each carbon of the double
bond.
• If the groups of higher priority are on the same side of
the double bond, the configuration is Z (German:
zusammen, together).
• If the groups of higher priority are on opposite sides of
the double bond, the configuration is E (German:
entgegen, opposite).
27
27
Configuration: E,Z
• Priority rules
1. Priority is based on atomic number; the higher the atomic number,
the higher the priority.
2. If priority cannot be assigned on the basis of the atoms bonded directly

to the double bond, look to the next set of atoms; priority is assigned at
the first point of difference.
28
28
14
Configuration - E,Z
3. Atoms participating in a double or triple bond are considered
to be bonded to an equivalent number of similar atoms by
single bonds.
29
29
Configuration - E,Z
• Example: name each alkene and specify its configuration by
the E,Z system
Cl
Cl
(a) (b) (c)
Cl
(d) (e)
Br
30
30
15
Which alkenes can exist as pairs of E/Z
isomers? For the ones that do, show E isomers
a) CH2=CHBr b) CH3CH=CHBr
c) (CH3)2C=CHCH3 d) (CH3)2CHCH=CHCH3
31
31
ALKENES & ALKYNES

PHYSICAL PROPERTIES
32
32
16
Properties of Alkenes
• The boiling point of each alkene is very similar to that of the
alkane with the same number of carbon atoms. Ethene,
propene and the various butenes are gases at room
temperature. All the rest that you are likely to come across
are liquids.
• In each case, the alkene has a lower boiling point than the
corresponding alkane. The only attractions involved are
dispersion forces, and these depend on the shape of the
molecule and the number of electrons it contains. Each
alkene has 2 fewer electrons than the alkane with the same
number of carbons.
• Alkenes are virtually insoluble in water, but dissolve in
organic solvents.
33
33
Physical Properties
• Alkenes and alkynes are nonpolar compounds.
• The only attractive forces between their molecules are
dispersion forces.
• The physical properties of alkenes and alkynes are
similar to those of alkanes of similar carbon
skeletons.
• Those that are liquid at room temperature are less
dense than water (1.0 g/mL).
• They dissolve in each other and in nonpolar organic
solvents.
• They are insoluble in water.
34
34
17
ALKENES & ALKYNES
ALKYNES (ACIDITY OF 1-ALKYNES)
35
35
Structure of Alkynes
• The functional group of an alkyne is a carbon-
carbon triple bond.
• A triple bond consists of:
• One s bond formed by the overlap of sp hybrid orbitals.
• Two p bonds formed by the overlap of sets of parallel 2p
orbitals.
36
36
18
Recall: Alkynes (CnH2n-2)

identifier.
alkynes.
37
37
The Acidity of Terminal Alkynes

• One of the major differences between the chemistry of alkynes, and
alkanes and alkenes is that the hydrogen atom of a terminal alkyne is
sufficiently acidic (pKa 25) that it can be removed by a strong base such
as sodium amide, NaNH2, to give an alkyne anion.
• Because water (pKa 15.7) is a stronger acid than acetylene or a terminal

alkyne, hydroxide ion is not a strong enough base for an acid-base
reaction with a terminal alkyne.
38
38
19
• The pKa values for alkane and alkene hydrogens are so large that no base
is strong enough to remove a hydrogen from either of these classes of
compounds.
• Anion stabilization is important

• The relevant anions are the ethynide anion (HC≡C-)- , in which carbon is
sp hybridized, the vinyl anion (H2C=CH-)- (trigonally or sp2 hybridized),
and the ethyl anion (H3C-CH2-)- (tetrahedrally or sp3 hybridized). The
former is the most stable and the last-named one is least stable.
39
Recall (Week 1): Bonding & hybridization

• Mixing one 2s orbital + one 2p orbital. The result must
be two sp hybrid orbitals.
40
40
20
• How do we account for the acidity of a terminal alkyne compared to an alkane
or alkene?
• We focus on the stability of the anion derived from each class of hydrocarbon.
• The lone pair of electrons of an alkane anion lies in an sp3 hybrid orbital,
which has 25% s character.
• For an alkene anion, the lone pair lies in an sp2 hybrid orbital, which has 33% s
character.
• For a terminal alkyne anion, the lone pair lies in an sp hybrid orbital, which
has 50% s character.
Recall (Week 1): Bonding and Hybridization

sp
sp3
41
41

• The greater the s character of the orbital bearing
the negative charge, the greater the stability of the
anion, and thus the greater acidic the hydrogen
removed.
• Of the series of compounds alkane, alkene, and
alkyne, the carbon of a terminal alkyne is the most
electronegative (50% s character). Therefore, a
terminal alkyne anion is the most stable of the
series, and a terminal alkyne is the most acidic.
42
42
21
The effect of Bonding on Acidity
Chemical Compounds CH3CH3 CH2=CH2 HC≡CH
Strength kJ/mol 420 444 552
pKa's 51 44 25
• The acidity of ethyne (acetylene) is much higher than that of ethene,

which is much greater than that of ethane.
• The bond strengths would predict the opposite effect, since the C-H bond
of ethyne is stronger than that of ethene than that of ethane. So, anion
stabilization effects must be operative.
• The relevant anions are the ethynide anion (HC≡C-)- , in which carbon is
sp hybridized, the vinyl anion (H2C=CH-)- (trigonally or sp2 hybridized),
and the ethyl anion (H3C-CH2-)- (tetrahedrally or sp3 hybridized). The
former is the most stable and the last-named one is least stable.
• It is very important to understand the reason for the profound difference
in acidity of C-H bonds as a function of their hybridization state. 43
43
22
MSE245
Organic Materials
WB 138
January 31, 2024

5. Reactions of Alkenes/Alkynes (Ch 5)
6. Chirality and the Shape of Molecules (handouts)
10. Amines (Ch 10)
1
Reactions of Alkenes and Alkynes
• Types of alkene reactions (5.1)

• Reaction mechanisms (5.2)
• Electrophilic addition reactions (5.3, 5.5)
• Carbocation rearrangements (5.4)
• Reduction of alkenes: formation of alkanes (5.6)
• Alkynes (5.7, 5.8)
REACTIONS OF ALKENES
TYPES OF ALKENE REACTIONS
2
Organic Reactions
• Organic reactions are chemical reactions involving organic
compounds
• In organic synthesis, organic reactions are used in the
construction of new organic molecules. The production of many
man-made chemicals (drugs, plastics, food additives, fabrics,
etc.) depend on organic reactions
• Many, many ways to classify organic reactions
• By reactions invented by a specific person (“named reaction”), ~1000s
• By type of organic reagent required in a specific transformation
• By mechanistic class/mechanism
• Addition reactions
• Elimination reactions
• Substitution reactions
• Rearrangement reactions
• Other
https://en.wikipedia.org/wiki/Organic_reaction
Recall: Alkenes & alkynes contain a C-C p bond


3
Characteristic Reactions of Alkenes
• Most characteristic reaction of alkenes is addition to the C=C
such that the p bond is broken and, in its place, s bonds are
formed to 2 new atoms/groups of atoms
Hydrochlorination
(hydrohalogenation)
Hydroboration
Hydration
Hydrogenation
(reduction)
Bromination
(halogenation)
Alkene Addition Reaction

• Two reactants add together to form a single new product with
no atoms “left over”
4
Low MW alkenes can be reacted to
produce chain-growth polymers
• In the presence of catalysts (‘initiators’), alkenes can form
polymers by the addition of monomers to a growing polymer
chain
initiator
nth
reaction
(Ethene) Poly(ethene)
REACTION MECHANISMS
10
5
A reaction mechanism is a step-by-step
description of how a reaction occurs
• It describes:
• Which bonds break and which new ones form.
• The order and relative rates of the various bond-breaking
and bond-forming steps.
• If the reaction takes place in solution, the role of the
solvent.
• The role of the catalyst (if one is present).
• The energy of the entire system during the reaction.
• A reaction mechanism is NOT a list of reagents or of
experimental conditions that bring about the chemical
transformation.
11
Energy diagram: A graph of the energy changes that occur during a

chemical reaction; energy is plotted on the y-axis. Reaction
progress on the x-axis.
Transition state: An unstable species of Activation energy Ea: The
maximum energy formed during the course of difference in energy between
a reaction; a maximum on an energy diagram. the reactants and the transition
state.
• Ea determines the rate of
reaction.
• If the Ea is large, very few
molecular collisions occur
with sufficient energy to
reach the transition state, and
the reaction is slow.
• If the Ea is small, many
collisions generate sufficient
energy to reach the transition
state, and the reaction is fast.
One-step exothermic reaction of C and A-B to give C-A and B
12
6
progress on the x-axis.
Transition state: An unstable species of
Heat of reaction DH: The
maximum energy formed during the course of difference in energy
a reaction; a maximum on an energy diagram. between reactants and
products.
• Exothermic reaction: A
reaction in which the
energy of the products is
lower than the energy of
the reactants; a reaction
in which heat is
liberated.
• Endothermic: A reaction
in which the energy of
the products is higher
than the energy of the
reactants: a reaction in
which heat is absorbed.
13
Energy diagram for a two-step exothermic reaction

involving formation of a reaction intermediate.
Reaction intermediate: An energy minimum between two transition steps.
Intermediates are highly reactive and rarely, if ever, can one be isolated.
Rate-determining step: The step in a reaction sequence that crosses the highest energy
barrier; the slowest step in a multistep reaction.
Two-step exothermic reaction involving the formation of a reaction intermediate
14
7
Why Mechanisms?
Mechanisms provide:
• A theoretical framework within which to
organize descriptive chemistry.
• An intellectual satisfaction derived from
constructing models that accurately reflect
the behavior of chemical systems.
• A tool with which to search for new
information and new understanding.
15
Developing a Reaction Mechanism

• Design experiments that will reveal the details of the particular
chemical reaction.
• Propose a set/sets of reaction steps that might account for the
overall chemical transformation.
• A mechanism becomes established when it is shown to be
consistent with every test that can be devised.
• This doesn’t mean that the proposed mechanism is correct, only
that it is the best explanation we are able to devise.
• A reaction mechanism uses the symbolism of a curved arrow to
show the redistribution of valence electrons that occurs as
covalent bonds are broken and new ones form. The next several
slides show the most common patterns that occur in the
reaction mechanisms we present in this text.
16
8
Recall (Week 1): The curved arrow is a symbol used
to show redistribution of valence electrons
• In using curved arrows, there are only two allowed

types of electron redistribution:
• from a bond to an adjacent atom.
• from an atom to an adjacent bond.
• Electron pushing by the use of curved arrows is a
survival skill in organic chemistry.
• learn it well!
17
Mechanism Patterns
• Before we discuss any particular reactions and their
mechanisms, let us first analyze several of the
common patterns to be seen in the mechanisms we
will encounter.
• Pattern 1: Add a Proton.
• Pattern 2: Take a proton away.
• Pattern 3: Reaction of an electrophile and a
nucleophile to form a new covalent bond.
• Pattern 4: Rearrangement of a bond.
• Pattern 5: Break a bond to form a stable molecule
or ion
18
9
Mechanism Pattern 1: Add a proton
• Pattern 1: Add a Proton. For example, curved arrows show the

redistribution of valence electrons and the formation of a new
covalent bond when a proton is transferred from acetic acid
(ethanoic acid) to ammonia.
19
Mechanism Pattern 1: Add a proton

• Pattern 1: Add a proton. In this example, a proton is added across
the p bond of a C—C double bond to form a new C—H bond.
Adding a proton is typical of all reactions that are catalyzed by an
acid.
• While it is most accurate to show proton transfer from H3O+ in

aqueous solution, we will often simplify the equation to show just
the proton H+ and the formation of a new covalent bond.
20
10
Mechanism Pattern 2: Take a proton away
• Pattern 2: Take a proton away. Reversing Pattern 1 corresponds to
taking a proton away. The mechanism for taking a proton away is
similar to that for adding a proton, except that we focus our
attention on the compound that loses the proton instead of the
compound that adds a proton.
Recall Pattern 1: Add a
proton
21
Mechanism Pattern 3: Electrophile +

nucleophile to form covalent bond
• Pattern 3: Reaction of an electrophile and a nucleophile
to form a new covalent bond.
• Electrophile: an electron-poor species that can accept a
pair of electrons to form a new covalent bond; a Lewis
acid.
• Nucleophile: an electron-rich species that can donate a
pair of electrons to form a new covalent bond, a Lewis
base.
E+ + Nu- à E:Nu
22
11
Are these electrophiles or nucleophiles?
OH NH3 H
I II III IV
23
Mechanism Pattern 4: Rearrangement of

a bond
• Pattern 4: Rearrangement of a bond. A
rearrangement occurs when the electrons of a s
bond break the bond from one atom and form a new
covalent bond to an adjacent atom.
24
12
Mechanism Pattern 5: Break a bond to
form a stable molecule/ion
• Pattern 5: Break a bond to form a stable molecule or
ion. A carbocation can be formed when a chemical
species breaks off from a molecule, taking the
electrons from the former single bond with it. The
chemical species formed is called the leaving group.
The bond breaks because doing so forms one or more
stable ions or molecules.
25
Carbocations (Carbon + cation)

• Carbocation: A species containing a C atom that has only 3
bonds to it, 6 electrons in its valence shell, and bears a positive
charge.
• Bond angles about the positively charged C are approximately 120°.
• C uses sp2 hybrid orbitals to form s bonds to the 3 attached groups.
• The unhybridized 2p orbital lies perpendicular to the s bond framework
and contains no electrons
• Carbocations are:
• Electrophiles: that is, they are electron-loving.
• Lewis acids: that is, they are electron-pair acceptors.
26
13
Recall (Week 1): Inductive effect
• Inductive polarization of electron density
transmitted through covalent bonds caused by a
nearby atom of higher electronegativity
27
Relative Stability of Carbocations

• Inductive effect: The polarization of the electron
density of a covalent bond as a result of the
electronegativity of a nearby atom.
• The electronegativity of a carbon atom bearing a positive
charge exerts an electron-withdrawing inductive effect
that polarizes electrons of adjacent s bonds toward it.
• Thus, the positive charge of a carbocation is not localized
on the trivalent carbon, but rather is delocalized over
nearby atoms as well.
• The larger the area over which the positive charge is
delocalized, the greater the stability of the cation.
28
14
The Inductive Effect
Tert-butyl cation
(Tertiary, 3° cation)
Methyl cation
29
Carbocations
• A 3° carbocation is more stable than a 2°
carbocation, and requires a lower activation energy
for its formation.
• A 2° carbocation is, in turn, more stable than a 1°
for its formation.
• Methyl and 1° carbocations are so unstable that
they are never observed in solution.
30
15
Example
Arrange these carbocations in order of increasing stability (least to
most).
H3C
I II III IV
31
ELECTROPHILIC ADDITION REACTIONS
32
16
Electrophilic addition reactions
• A π bond is a region of high electron density (in red), so alkenes are
typically nucleophiles.
• Alkenes typically undergo addition reactions in which the π bond is
converted to two new σ bonds
• Addition of hydrogen halides (HCl, HBr, HI) –
Hydrochlorination/Hydrohalogenation
Br
CH3-CH=CH2 + HBr CH3-CH-CH3
• Addition of water (H2O/H2SO4) - Hydration
OH
H2SO4
CH3-CH=CH2 + H 2O CH3-CH-CH3
• Addition of halogens (Cl2, Br2) - Halogenation
Br Br
CH3-CH=CH2 + Br2 CH3-CH-CH2
33
Addition of Hydrogen Halides

(Hydrochlorination, hydrohalogenation)
• Carried out with the pure reagents or in a polar solvent such as acetic
acid.
• Addition is regioselective.
• Regioselective reaction: A reaction in which one direction of bond forming
or bond breaking occurs in preference to all other directions.
• Markovnikov’s rule: In additions of HX to a double bond, H adds to the

carbon with the greater number of hydrogens already bonded to it.
34
17
Markovnikov’s Rule
• The chemical basis for the regioselectivity embodied in
Markovnikov’s rule lies in the relative stabilities of carbocation
intermediates. The reason why the proton of H—X adds to the
less substituted carbon of the double bond is that this mode of
addition leads to the more stable carbocation intermediate.
35
Example
36
18
Regioselectivity
• Markovnikov’s rule is but one example of regioselectivity.
There will be more examples in this and later chapters.
37
Addition of HCl to 2-Butene

• A two-step mechanism
• Step 1: Add a proton. Formation of a sec-butyl cation, a 2°
carbocation intermediate.
• Step 2: Reaction of an electrophile and a nucleophile to

form a new covalent bond. Reaction of the sec-butyl cation
(an electrophile) with chloride ion (a nucleophile) completes
the reaction.
38
19
Energy diagram for the two-step exothermic addition of HCl
to 2-butene
39
Summary of addition of HX to alkenes

• When treated with HX, alkenes form alkyl halides (haloalkanes).
• Hydrogen halide reactivity order: HI > HBr > HCl > HF (paralleling
acidity order) (mostly HCl and HBr). (Recall from Week 1)
• Regioselectivity predicted by Markovnikov's rule :
"For addition of hydrogen halides to alkenes, the H atom adds to
the C with the most H atoms already present."
• Reaction proceeds via protonation to give the more stable
• Not stereoselective since reaction proceeds via planar
carbocation.
40
20
Example 5.2
41
Addition of H2O to an Alkene (Hydration)

• Acid-catalyzed hydration of an alkene is regioselective:
hydrogen adds preferentially to the less substituted
carbon of the double bond. Thus H–OH adds to alkenes
in accordance with Markovnikov's rule.
42
21
• Step 1: Add a proton. Proton transfer from the acid catalyst
(H3O+) to propene gives a 2° carbocation intermediate.
• Step 2: Reaction of a nucleophile and an electrophile to form a

new covalent bond. Reaction of the carbocation intermediate
with water completes the valence shell of carbon and gives an
oxonium ion.
43
• Step 3: Take a proton away. Proton transfer from

the oxonium ion to water gives the alcohol and
regenerates the acid catalyst.
44
22
Summary of addition of H2O to an alkene
(Hydration)
• When treated with aqueous acid, most commonly H2SO4,
alkenes form alcohols.
• Regioselectivity predicted by Markovnikov's rule
• Reaction proceeds via protonation to give the more stable
• Not stereoselective since reactions proceeds via planar
carbocation.
45
Example 5.6: Propose a mechanism for the acid-catalyzed hydration

of methylenecyclohexane to give 1- methylcyclohexanol.
46
23
Addition of Cl2 and Br2 (Bromination,
halogenation)
• Carried out with either the pure reagents or in an

inert solvent such as CH2Cl2.
47
Addition of Cl2 and Br2 (Bromination,

halogenation)
• Addition is stereoselective.
• Stereoselective reaction: A reaction in which one
stereoisomer is formed or destroyed in preference to all
others that might be formed or destroyed.
• Addition to a cycloalkene, for example, gives only a trans
product. The reaction occurs with anti stereoselectivity.
48
24
Mechanism of addition of Cl2 and Br2
• Step 1: Reaction of a nucleophile and an electrophile to form a new
covalent bond. Reaction of the p bond (a nucleophile) with bromine (an
electrophile) gives a bridged bromonium ion intermediate
• Step 2: Reaction of a nucleophile, and an electrophile to form a new

covalent bond. Attack of bromide ion from the side opposite the
bridged bromonium ion opens the three-membered ring.
49
Summary of Addition of Cl2 and Br2

(Bromination, halogenation)
• Overall transformation: C=C to X-C-C-X
• Reagent: normally the halogen (e.g. Br2) in an inert solvent like
methylene chloride, CH2Cl2.
• Regioselectivity: not relevant since both new bonds are the
same, C-X.
• Reaction proceeds via cyclic halonium ion.
• Stereoselectivity: anti since the two C-X bonds form in
separate steps one from X2 the other X-.
50
25
Example
51
CARBOCATION REARRANGEMENTS
52
26
Carbocation Rearrangements
• The product of electrophilic addition to an alkene involves
rupture of a p bond and formation of two new s bonds in its
place. In the following addition only 17% of the expected
product is formed.
• Rearrangement: A reaction in which the connectivity of atoms
in the product is different from that in the starting material.
53
• In the rearrangements we examine, typically either
an alkyl group or a hydrogen atom migrates with its
bonding electrons from an atom to an adjacent
electron-deficient atom as illustrated in the
following mechanism. The key step in this type of
rearrangement is called a 1,2-shift.
54
27
• Step 1: Add a proton. Proton transfer from HCl to the
alkene to give a 2° carbocation intermediate.
• Step 2: Rearrangement of a bond. Migration of a methyl

group with its bonding electrons from the adjacent carbon
gives a more stable 3° carbocation.
55
• Step 3: Reaction of a nucleophile and an
electrophile to form a new covalent bond.
Reaction of the 3° carbocation (an electrophile and
a Lewis acid) with chloride ion (a nucleophile and a
Lewis base) gives the rearranged product.
56
28
• Rearrangements also occur during the acid-
catalyzed hydration of alkenes, especially where the
carbocation formed in the first step can rearrange to
a more stable carbocation.
57
Carbocations—Summary
• The carbon bearing a positive charge is sp2 hybridized
with bond angles of 120° about it.
• The order of carbocation stability is 3°>2°>1°.
• Carbocations are stabilized by the electron-withdrawing
inductive effect of the positively charged carbon.
• Methyl and 1° carbocations are so unstable that they
are never formed in solution.
• Carbocations may undergo rearrangement by a 1,2-
shift, when the rearranged carbocation is more stable
than the original carbocation. The most commonly
observed pattern of rearrangement is from 2° to 3°.
58
29
Carbocations—Summary
• Carbocation intermediates undergo three types of
reactions:
1. Rearrangement by a 1,2-shift to a more stable
carbocation.
2. Addition of nucleophile to form a new covalent bond
(e.g., halide ion, H2O, Br–).
3. Loss of a proton to give an alkene (the reverse of the
first step in both the addition of HX and the acid-
catalyzed hydration of an alkene).
59
REDUCTION OF ALKENES: FORMATION OF ALKANES
60
30
Oxidation Reactions of Alkenes
• Oxidation: addition of O to, or removal of H, from a carbon atom
(increases the number of C-O bonds or decreases the number of C-
H bonds)
• Reduction: removal of O from, or addition of H, to a carbon atom
(increases the number of C-H bonds or decreases the number of C-
O bonds)
Relative oxidation state of some common organic functional groups

H
H
H
61

• Example: Conversion of the C=C double bond to 1,2-diol (an
alcohol with 2 hydroxyl (-OH) groups on adjacent carbon atoms,
glycol)
• Oxidative addition reaction of alkenes (1,2-Dihydroxylation)
• Osmium tetroxide (OsO4) is a widely used oxidizing agent
62
31
• Oxidation by OsO4 converts an alkene to a glycol, a compound with -OH groups
on adjacent carbons
• Oxidation is syn stereoselective – forming cis- product
Syn relationship: when 2 atoms are added to the same side
Anti relationship: when 2 atoms added to opposite sides
Dihydroxylation with Osmium Tetroxide (OsO4)

A cyclic osmate ester
https://www.masterorganicchemistry.com/2011/07/01/reagent-friday-oso4-osmium-tetroxide/
63
Reduction of Alkenes
• Alkenes react with H2 in the presence of a
transition metal catalyst to give alkanes.
• The most commonly used catalysts are Pd, Pt, and Ni.
• The reaction is called catalytic reduction or catalytic
hydrogenation.
64
32
Reduction of Alkenes
• The most common pattern is syn addition of hydrogens;
both hydrogens add to the same side of the double bond.
• Catalytic reduction is syn stereoselective.
65
Catalytic Reduction of an Alkene

• Syn addition of H2 to an alkene involving a
transition metal catalyst.
• (a) H2 and the alkene are absorbed on the catalyst.
• (b) One H is transferred forming a new C-H bond.
• (c) The second H is transferred. The alkane is released.
66
33
Heats of Hydrogenation
These exothemic reactions form the basis of experimental "heats of
hydrogenation" to establish the stability of isomeric alkenes.
67
• Reduction involves net conversion of a weaker p
bond to a stronger s bond.
• The greater the degree of substitution of a double
bond, the lower its heat of hydrogenation.
• The greater the degree of substitution, the more stable
the double bond.
• The heat of hydrogenation of a trans alkene is
lower than that of an isomeric cis alkene.
• A trans alkene is more stable than its isomeric cis
alkene.
• The difference is due to nonbonded interaction strain in
the cis alkene.
68
34
• Heats of hydrogenation of cis-2-butene and trans-2-
butene.
• trans-2-butene is more stable than cis-2-butene by 4.2
kJ/mol.
69
Additional Example
70
35
REACTIONS OF ALKYNES
ALKYNES
71
Recall: Acidity of Terminal Alkynes

• As we saw in Chapter 4, one of the major differences
between the chemistry of alkanes, alkenes, and
alkynes is that terminal alkynes are weak acids.
72
36
Alkylation of Terminal Alkynes
• Treatment of a 1-alkyne with a very strong base
such as sodium amide, NaNH2, converts the alkyne
to an acetylide anion.
73
Reduction of Alkynes
• Treatment of an alkyne with H2 in the presence of a
transition metal catalyst, most commonly Pd, Pt, or
Ni, results in addition of two moles of H2 and
conversion of the alkyne to an alkane.
74
37
Characteristic Reactions
H
C C + HCl C C hydrochlorination
Cl (hydrohalogenation)
H
H+
C C + H2 O C C hydration
OH
Br
C C + Br 2 C C bromination
H Br (halogenation)
C C + OsO4 C C oxidation
OH OH (hydrogenation)
C C + H2 C C reduction
H H (hydrogenation)
75
Polymerization of Alkene
76
38
MSE245
Organic Materials
WB 138
February 2, 2024

10. Amines (Ch 10)
2
1
SHAPE OF MOLECULES
ISOMERS, STEREOCENTERS, CHIRALITY, SYMMETRY
Isomers are different compounds with

the same molecular formulas
• Isomers reflect the extraordinary versatility of carbon in forming
strong bonds to itself and to other elements
• All isomers are either constitutional isomers or stereoisomers
Constitutional isomers
Stereoisomers
(Structural isomers)
Isomers which have the same
Isomers which differ in "connectivity” connectivity (i.e., more subtle kind
(i.e., the difference is in the sequence of isomerism, the isomers differ
in which atoms are attached to one only in their spatial arrangement,
another). not in their connectivity).
e.g., C5H12
2
Constitutional isomers vs. Stereoisomers
Although constitutional isomers have the same molecular

formula, their physical and chemical properties may be
very different.
3
Geometrical Optical
ISOMERS
CONSTITUTIONAL (STRUCTURAL) ISOMERS
4
Constitutional (Structural) Isomers
• When the group of atoms that make up the molecules of
different isomers are bonded together in fundamentally different
ways, we refer to such compounds as constitutional isomers
(structural isomers).
• have the same molecular formula.
• have different bond connectivities.
• are different compounds.
• have unique names.
• have different physical properties.
• may or may not have similar chemical properties.
• There are 3 types of constitutional isomers:
• Chain (or nuclear) isomers
• Position isomers
• Functional group isomers
Chain (Nuclear) Isomers

• These isomers arise because of the possibility of
branching in carbon chains. For example, there are two
isomers of butane, C4H10. In one of them, the carbon
atoms lie in a "straight chain" whereas in the other the
chain is branched.
10
10
5
Position Isomers
• Position isomers have the same carbon skeleton and the same
substituent groups, but differ in the position of the substituent
group
• Position isomers occur among substituted alkanes and other
compounds. They have similar chemical properties since they
differ only in the location of the functional group
• This is an important group in cyclic compounds
11
11
Functional Isomers
• They have the same molecular formula but differ in the nature
of the functional group.
• e.g: Dimethyl Ether: (CH3)2O and Ethanol: C2H5OH.
• Even though the atoms are the same, they are arranged differently. This
yields two different compounds with the same number of atoms. These
compounds have different functional groups. They are functional
isomers (belong to constitutional isomers).
• The first is a gas which will knock you out if inhaled. The other is
common alcohol drunk in spirits. The two molecules are shown below.
Dimethyl Ether Ethanol
12
12
6
Structural Formulas for C4H10O Isomers (total of 7 isomers)
Kekulé Formula Condensed Formula Line-angle Formula
Alcohols
Ethers
There are no double or triple bonds and no rings in any of these structures 13
13
Which one is the same or different?
14
14
7
ISOMERS
STEREOISOMERS
15
15
Stereoisomers
• There are two major types of stereoisomers:

1. Diastereomers (or Geometrical isomers) and
2. Enantiomers (or Optical isomers)
• Diastereoisomers: Stereoisomers which are not mirror images
• Cis- and trans-isomers are a type of diastereomers. They have
the same connectivity but are not mirror images of each other.
• Enantiomers: Stereoisomers which are mirror images
• The difference between diastereoisomers and enantiomers rests
upon the concept of mirror image isomerism.
16
16
8
Geometric (cis/trans) isomerism
(disasteromers)
• Geometric isomers have the same structural formulas but differ in the
arrangement of groups at a single atom, at double bonds, or in rings.
isomer melting point (°C) boiling point (°C)

cis -80 60
trans -50 48
17
17
Properties of cis- vs. trans- Isomers

• cis-isomer has a higher boiling point
• trans-isomer has a higher melting point
Isomer Melting point (°C) Boiling point (°C)

cis-1,2-dichloroethene -80 60
trans-1,2-dichloroethene -50 48
Isomer Melting point (°C) Boiling point (°C)

cis-but-2-ene -139 4
trans-but-2-ene -106 1
Note: This Tb difference is distinct from what we saw in constitutional isomers in alkanes
(previous lecture) 18
18
9
Why is the boiling point of the cis-isomers
higher?
• There are stronger intermolecular forces between the molecules of
the cis-isomers than between trans-isomers in the liquid phase.
• Both isomers have exactly the same atoms joined up in exactly the same
order (i.e., the van der Waals dispersion forces between the molecules will be
the same).
• The difference is that the cis-isomer is a polar molecule whereas the trans-
isomer is non-polar.
• Both molecules contain polar chlorine-carbon bonds, but in the cis-isomer
they are both on the same side of the molecule. That means that one side of
the molecule will have a slight negative charge while the other is slightly
positive. The molecule is therefore polar.
• There will be dipole-dipole interactions as well as dispersion forces - needing
extra energy to break
e.g., 1,2-dichloroethene
19
19
Why is the melting point of the trans-isomers

higher?
• In order for the intermolecular forces to work well in the
solid phase, the molecules must be able to pack together
efficiently in the solid.
• Trans-isomers pack better than cis-isomers. The "U" shape
of the cis-isomer doesn't pack as well as the straighter
shape of the trans-isomer.
• The poorer packing in the cis-isomers means that the
intermolecular forces aren't as effective as they should be
and so less energy is needed to melt the molecule - a lower
melting point.
20
20
10
Enantiomers (optical isomers) - Chirality
• A molecule or object which is not identical to (i.e., non-superimposable upon)
its mirror image molecule or object is said to be chiral. This means it resembles
a human hand in that the left and right hands are not superimposabile but can
be readily distinguished.
• To be isomers, molecules must not be identical. The test for "identicality" is
one of superimposability.
• Many molecules are chiral, especially complex molecules such as those found in
biological systems.
21
21
Stereogenic (Chiral) Center

How can you anticipate if a molecule is chiral (has an enantiomer)
or is achiral (has no enantiomer)?
• One of the simple ways is to use the concept of a stereogenic
(chiral) center. If a molecule has a single stereogenic center it
will necessarily be chiral. The most common kind of stereogenic
center is a carbon (or other atom) which has four different
atoms or groups directly attached to it.
22
22
11
Chirality and Stereocenter
• The most common cause of chirality is the presence of a carbon atom bonded
to 4 different groups.
• Such carbon is referred as chirality center or stereocenter.
• Chirality is the property of the entire molecule, a stereocenter is the cause of
chirality.
23
23
Tetrahedral carbon and their mirror images
24
24
12
Symmetry Elements
• If the molecule or object has either a plane of symmetry or a
center of symmetry it is achiral (non-chiral).
• It is especially useful when there is more than one
stereocenter.
25
25
26
26
13
Example
• Is 5-bromodecane chiral?
• If so, identify the stereocenter
27
27
14
MSE245
Organic Materials
WB 138
February 14, 2022

10. Amines (Ch 10)
2
1
Substitution & Elimination Reactions
• In this chapter, we concentrate on two types of reactions:
• Nucleophilic substitution – any reaction in which one nucleophile is
substituted for another
• b-elimination – removal of atoms/group of atoms from 2 adjacent C atoms
• Because all nucleophiles are also bases, nucleophilic substitution
and base-promoted b-elimination are competing reactions
• In the presence of a strong base, halogen can be removed from

one carbon of a haloalkane and hydrogen from an adjacent
carbon to form a C=C double bond 3
Chapter 7
• Introduction and nomenclature (short review) (7.1)

• Nucleophilic Aliphatic Substitution and β-Elimination
(7.2)
• Nucleophilic Aliphatic Substitution (7.3)
• Mechanisms of Nucleophilic Aliphatic Substitution: SN1
and SN2 mechanisms (7.4)
• SN1 and SN2 dominating factors & experimental
conditions (7.5, 7.6)
• β-Elimination (7.7)
• Mechanism of β-Elimination, E1 or E2? (7.8)
• Substitution vs. Elimination (7.9)
2
HALOALKANES
b-ELIMINATION
Recall: Characteristic Reactions of Alkenes

Hydrochlorination
(hydrohalogenation)
Hydroboration
Hydration
Hydrogenation
(reduction)
Bromination
(halogenation)
3
Recall: Hydrohalogenation (hydrochlorination), a
mechanism of electrophilic addition
• Electrophilic addition happens in many of the reactions
of alkenes, containing carbon-carbon double bonds
b-Elimination
• b-Elimination: removal of atoms or groups of atoms
from adjacent carbons to form a carbon-carbon double
bond
• we study a type of b-elimination called dehydrohalogenation
(the elimination of HX)
b a
C C + CH3 CH2 O-Na+
CH 3 CH 2 OH
H X
Base
An alkyl
halide
C C + CH3 CH2 OH + Na+ X -
An alkene
8
4
b-Elimination
• Zaitsev’s rule: The major product of a b-elimination
is the more stable (the more highly substituted)
alkene. When cis-trans isomerism is possible, the
trans isomer is favored.
Example (Problem 7.6)

Predict the b-elimination products formed when each
chloroalkane is treated with sodium ethoxide in ethanol:
10
10
5
b-Elimination mechanisms
There are two limiting mechanisms for b-elimination
reactions
• E1 mechanism: at one extreme, breaking of the C-X
bond is complete before reaction with base breaks the C-H
bond
• Only R-X is involved in the rate-determining step
• Rate = k[haloalkane]
• E2 mechanism: at the other extreme, breaking of the C-
X and C-H bonds happens at the same time
• Both R-X and base are involved in the rate-determining
step
• Rate = k[haloalkane][base]
11
11
Elimination Reaction Mechanism

• Elimination reaction between a simple haloalkane like 2-
bromopropane and hydroxide ions (from, for example,
sodium hydroxide) to give an alkene.
• In elimination reactions, the hydroxide ion acts as a base -
removing a hydrogen as a hydrogen ion from the carbon
atom next to the C holding the bromine.
• The resulting re-arrangement of the electrons expels the
bromine as a bromide ion and produces propene.
12
12
6
E1 Mechanism
• Step 1: Break a bond to give a stable molecule or ion.
Rate-determining ionization of C-X gives a carbocation
intermediate and halide ion.
• Step 2: Take a proton away. Proton transfer from the

carbocation to a base (in this case, the solvent) gives
the alkene.
13
13
Elimination 1 (E1) Mechanism (vs SN1)

• E1 happens at a similar condition as SN1.
• The E1 and SN1 are, in fact, in competition whenever
an alkyl halide is treated in a hydroxylic solvent with a
non-nucleophilic base.
• The best substrate (secondary and tertiary) for E1 is
also the best for SN1, and a mixture of products is
obtained.
14
14
7
15
15
E2 Mechanism
• A one-step mechanism; all bond-breaking and
bond-forming steps are concerted. Simultaneously
(1) take a proton away and (2) break a bond to form
a stable ion or molecule.
16
16
8
Elimination Bimolecular (E2) Mechanism
• When a base reacts with an alkyl halide, nucleophile/base can substitute for the
leaving group in an SN(1 or 2) to ELIMINATE HX leading to formation of an
alkene.
• Elimination reaction almost always get mixtures of alkene products
• According to Zaitsev’s rule, In the elimination of HX from an alkyl halide, the
more highly substituted alkene product predominates.
• E2 is the most common occurring mechanism.
• Like SN2, E2 occurs at 1 step without intermediates.
• The leaving group takes 2 electrons from the former C-X bond
17
17
18
18
9
HALOALKANES
MECHANISMS OF b-ELIMINATION: E1 OR E2
19
19
Summary of E1 versus E2 Reactions for

Haloalkanes
20
20
10
Example
What is the major product from an elimination reaction

starting with 2-bromopentane?
a) 1-pentene
b) cis-2-pentene
c) trans-2-pentene
d) a mixture of cis and trans-2-pentene
21
21
Example 7.7
Predict whether each b-elimination reaction proceeds
predominantly by an E1 or E2 mechanism, and write a structural
formula for the major organic product
22
22
11
Example
1) Identify the major product(s) for the following reaction
2) State the reaction type
I
NaOCH2CH3
CH3CH2OH
23
23
HALOALKANES
SUBSTITUTION VS b-ELIMINATION
24
24
12
• In Chapter 7, we learned of two types of reactions:
• Substitution reactions allows compounds (e.g., haloalkanes) to be converted to

compounds with other functional groups (alcohols, ethers, thiols, sulfides, amines,
nitriles, alkenes, alkynes…) and vice versa
• Elimination reactions allow In the presence of a strong base, functional group (e.g.,
a halogen) can be removed from one C of a haloalkane and hydrogen from an
adjacent C to form a C=C double bond 25
25
Summary of SN1 and SN2 Reactions of Haloalkanes
26
26
13
Summary of E1 versus E2 Reactions for
Haloalkanes
27
27
Recall (last week): Relative Nucleophilicity
28
28
14
Recall (Week 1): Lewis Acids and Bases
29
29
Substitution versus Elimination

• Because many nucleophiles are also strong bases (OH–
and RO–), SN and E reactions often compete.
• The ratio of SN/E products depends on the relative rates of
the two reactions.
• In general, the major barriers for:
• SN2 – Steric hindrance
• SN1/E1 - Carbocation Stability
• E2 - No “big barrier”
30
30
15
SN1 versus E1
• Reactions of 2° and 3° haloalkanes in polar protic
solvents give mixtures of substitution and elimination
products. Product ratios are difficult to predict.
• Often the same products with different kinetics
31
31
SN2 versus E2
• It is considerably easier to predict the ratio of SN2 to
E2 products.
• Branching made E2 products (alkenes) more stable
• Strong Nu: favors SN2; Strong base favors E2.

32
32
16
Summary of Mechanisms
• We have seen a total of 4 nucleophilic substitution/
elimination reactions. How do you predict what reaction
will take place?
• A primary substrate (RCH2X) reacts by an SN2 mechanism with
good nucleophiles such as I-, Br-, RS-, NH3 or CN-, or E2 attacked
by strong base such as hydroxide ion or an alkoxide ion (RO-, e.g
EtO-)
• A secondary substrate (R2CHX) react by both SN2 and SN1 (or E1
and E2) to give a mixture of substitution and elimination
products
• A tertiary substrate (R3CX) reacts by an E2 pathway if a strong
base is used or by a mixture of SN1 and E1 under neutral or acidic
conditions.
33
33
Summary of SN versus E for methyl and

primary haloalkanes
EtO-
34
17
Summary of SN versus E for secondary or
tertiary haloalkanes
35
S vs E for Haloalkanes: Predict the major product and

the mechanism for each reaction
(Hint: substrate, nucleophile/base, solvent)
Cl 80°C
1. + NaOH
H 2O
30°C
2. + (C2 H5) 3N
Br CH2 Cl2
Br
- +
3. + CH3O Na
methanol
Cl
+ -
4. + Na I
acetone
36
36
18
37
37
19
MSE245
Organic Materials
WB 138
February 7, 2024
Course update
• Midterm exam: Friday, Feb 9, 2024, 9-10 am
• Held in BA1130
• It will cover up to the end of what we covered in
last week’s lectures (Chirality and Shape of
Molecules)
• Please bring your student ID and a non-
programmable calculator
• Otherwise, no aids are allowed
1
10. Amines (Ch 10)
3
Chapter 7
• Introduction and nomenclature (short review) (7.1)

• Nucleophilic Aliphatic Substitution and β-Elimination
(7.2)
• Nucleophilic Aliphatic Substitution (7.3)
• Mechanisms of Nucleophilic Aliphatic Substitution: SN1
and SN2 mechanisms (7.4)
• SN1 and SN2 dominating factors & experimental
conditions (7.5, 7.6)
• β-Elimination (7.7)
• Mechanism of β-Elimination, E1 or E2? (7.8)
• Substitution vs. Elimination (7.9)
2
HALOALKANES
INTRODUCTION & NOMENCLATURE (REVIEW)
Recall (from IUPAC lecture): Haloalkanes

(alkyl halides)
• Haloalkane (alkyl halide): A compound containing a
halogen atom covalently bonded to an sp3 hybridized
carbon.
• given the symbol RX
• Halogens: F, Cl, Br, I
3
Recall: Nomenclature - IUPAC
• Locate the parent alkane.
• Number the parent chain to give the substituent encountered first the
lower number.
• Show halogen substituents by the prefixes fluoro-, chloro-, bromo-, and
iodo- and list them in alphabetical order with other substituents.
• Locate each halogen on the parent chain.
Recall: Nomenclature
• Several polyhaloalkanes are common solvents and
are generally referred to by their common or trivial
names.
4
Freons & their Alternatives
• Freons are chlorofluorocarbons (CFCs)
• Among the most widely used are/were:
• Much lower ozone-depleting alternatives are the

hydrofluorocarbons (HFCs) and the
hydrochlorofluorocarbons (HCFCs), including:
Recall (last week): Characteristic Reactions of

Alkenes
10
10
5
Formation of haloalkanes (alkyl halides)
Methane Chloromethane
11
11
Formation of haloalkanes (alkyl halides)

Most common preparation method is from reacting an
alcohol with a strong acid (hydrogen halide, HX); Chapter 8
12
12
6
Recall: Organic Reactions
• Organic reactions are chemical reactions involving organic
compounds
• In organic synthesis, organic reactions are used in the
construction of new organic molecules. The production of many
man-made chemicals (drugs, plastics, food additives, fabrics,
etc.) depend on organic reactions
• Many, many ways to classify organic reactions
• By reactions invented by a specific person (“named reaction”), ~1000s
• By type of organic reagent required in a specific transformation
• By mechanistic class/mechanism
• Addition reactions
• Elimination reactions
• Substitution reactions
• Rearrangement reactions
• Other
https://en.wikipedia.org/wiki/Organic_reaction 13
13
Haloalkanes (Alkyl Halides)

Functional group suffix = -halide
Functional group prefix = halo-
Structure:
• The alkyl halide functional group consists of an sp3 hybridised C atom bonded to a halogen,
X, via a σ bond.
• The carbon-halogen bonds are typically quite polar due to the electronegativity and
polarizability of the halogen.
Physical Properties:
• The polar bond creates a molecular dipole that raises the melting points and boiling points
compared to alkanes.
Reactivity:
• Can undergo 2 major kinds of reactions: substitution and/or elimination
• The halogens (Cl, Br and I) are good leaving groups (chemical species that breaks off from a
molecule, taking the electrons from the former single bond with it)
• The polarity makes the C atom electrophilic and prone to be attacked by nucleophiles via
substitution reactions (i.e., SN1 or SN2 reactions).
• Bases can remove β-hydrogens and cause 1,2-elimination to form alkenes (i.e., via E1 or E2
reactions).
• Insertion of a metal (especially Mg) creates an organometalic species. 14
14
7
Recall (last week): Mechanism Patterns: Electrophile
+ nucleophile to form covalent bond
• Electrophile: an electron-poor species that can accept a pair

of electrons to form a new covalent bond; a Lewis acid.
• Nucleophile: an electron-rich species that can donate a pair
of electrons to form a new covalent bond, a Lewis base.
E+ + Nu- à E:Nu
15
15
HALOALKANES
NUCLEOPHILIC ALIPHATIC SUBSTITUTION AND b-ELIMINATION
16
16
8
• In this chapter, we concentrate on two types of reactions:
• This allows haloalkanes to be converted to compounds with other

functional groups (alcohols, ethers, thiols, sulfides, amines,
nitriles, alkenes, alkynes…) 17
17
HALOALKANES
NUCLEOPHILIC ALIPHATIC SUBSTITUTION
18
18
9
Nucleophilic Substitution
• In the following general reaction, substitution takes
place on an sp3 hybridized (tetrahedral) carbon.
Halide ions are among the best and most important leaving groups
(chemical species that breaks off from a molecule, taking the
electrons from the former single bond with it)
19
19
Nucleophilic Substitution reactions

• Nucleophilic substitution reactions are an important class of reactions that allow
the interconversion of functional groups, for example R-Br→ R-OH.
• What does the term "nucleophilic substitution" imply?
• A nucleophile is an electron rich species that will react with an electron poor species.
• A substitution implies that one group replaces another
• There are two fundamental events in these substitution reactions:

• formation of the new bond to the nucleophile
• breaking of the bond to the leaving group
• Depending on the relative timing of these events, two different mechanisms are
possible:
• Bond breaking to form a carbocation precedes the formation of the new bond: SN1
reaction
• Simultaneous bond formation and bond breaking: SN2 reaction 20
20
10
Nucleophilic substitution
• Carbon-halogen bond, and all the nucleophilic substitution reactions
of the halogenoalkanes, involve breaking that bond.
• With the exception of iodine, all of the halogens are more
electronegative than carbon.
• Electronegativity values: C=2.5, F=4.0, Cl=3.0, Br=2.8, I=2.5
• The electron pair in the carbon-halogen bond will be dragged
towards the halogen end, leaving the halogen slightly negative (-)
and the carbon slightly positive (+) (except in the carbon-iodine
case).
• Although the carbon-iodine bond doesn't have a permanent dipole,
the bond is very easily polarized by anything approaching it. Imagine
a negative ion approaching the bond from the far side of the carbon
atom:
21
21
Recall (Week 1): Functional Groups

they are:
classes.
Haloalkanes are versatile molecules that can react with

nucleophiles to convert them to alcohols, ethers, thiols,
amines and alkenes
22
22
11
Nucleophilic Substitution
23
23
HALOALKANES
NUCLEOPHILIC ALIPHATIC SUBSTITUTION: SN1 AND SN2
MECHANISMS
24
24
12
Mechanism of SN1 and SN2
• Chemists proposed two limiting mechanisms for
nucleophilic displacement
• a fundamental difference between them is the timing of
bond breaking and bond forming steps
• At one extreme, the two processes take place
simultaneously; designated SN2
• In the other limiting mechanism, bond breaking
between carbon and the leaving group is entirely
completed before bond forming with the
nucleophile begins; designated SN1
25
25
SN2: Bond breaking & bond forming take

place simultaneously
• S = substitution
• N = nucleophilic
• 2 = bimolecular (two species (both reactants) are involved in the rate-
determining step)
• rate = k[haloalkane][nucleophile] or k [R-LG][Nu:]
The nucleophile attacks the reactive center

Both reactants are involved in from the side opposite the leaving group. The
the transition state of the rate- key step is reaction of a nucleophile and an
determining step. electrophile to form a new covalent bond. 26
26
13
Recall (last week): Energy diagrams
progress on the x-axis. Transition state: An unstable
species of maximum energy
formed during the course of a
reaction; a maximum on an
energy diagram.
Activation energy Ea: The

difference in energy between
the reactants and the
transition state.

27
27
Energy diagram for an SN2 reaction

• There is one transition state and no reactive intermediate
Both reactants are

involved in the transition
state of the rate-
determining step.
The nucleophile attacks

the reactive center from
the side opposite the
leaving group. The key
step is reaction of a
nucleophile and an
electrophile to form a
new covalent bond.
28
28
14
Steric Effects in SN2 Reactions
• Carbon accessibility is high on bromomethane –> fast SN2
reaction. This effect is successively reduced as below:
29
29
Steric Effects in SN2 Reactions

• The negative charge attacks C and kicks out the halogen group
• Vinylic (R2C=CRX) and aryl (Ar-X) halides are completely inactive due to
steric hindrance.
30
30
15
Leaving Group in SN2
• Since the LG is expelled from the SN2 reaction, the best LGs are those giving the
anions for stable acids.
• In all of these nucleophilic substitution reactions, the carbon-halogen bond has to
be broken at some point during the reaction. The harder it is to break, the slower
the reaction will be.
• The carbon-fluorine bond is very strong (stronger than C-H) and isn't easily broken,
thus fluoroalkanes are very unreactive. In the other halogenoalkanes, the bonds
get weaker as you go from chlorine to bromine to iodine.
C-H 413 C-F 467
C-Cl 346
C-Br 290
C-I 228
31
31
Example
Arrange the alkyl halides in order of increasing reactivity
in an SN2 reaction with KI in acetone (least first).
Cl
CH2CH2Br Cl CCH3 Br
CH3
I II III IV
32
32
16
Example
Which nucleophilic substitution reactions will proceed?
acetone
I. NaCl + CH3CH2OH
II. NH3 + Br ethanol
III. CH3CH2O + CH3CH2CH2Cl ethanol
acetone
IV. LiCl + CH4
33
33
SN1: Bond breaking between C and the leaving

group is completed before bond forming with
nucleophile begins
• S = substitution
• N = nucleophilic
• 1 = unimolecular (only one species is involved in the rate-determining step)
• rate = k[haloalkane]
• SN1 indicates a substitution, nucleophilic, unimolecular reaction,
described by the expression rate = k [R-LG] . The rate is governed by the
substrate only.
• This pathway is a multi-step process with the following characteristics:
• Step 1: rate-determining (slow) loss of the leaving group, LG, to generate a
carbocation intermediate, then
• Step 2: rapid attack of a nucleophile on the electrophilic carbocation to form a
new σ bond
• Reactivity order : (CH3)3C- > (CH3)2CH- > CH3CH2- > CH3-
• In an SN1 reaction, the key step is the loss of the leaving group to form
the intermediate carbocation. The more stable the carbocation is, the
easier it is to form, and the faster the SN1 reaction will be.
• it is the generation of the carbocation that is rate determining. 34
34
17
Recall (last week): Mechanism Patterns: Break
a bond to form a stable molecule/ion
• Pattern 5: Break a bond to form a stable molecule or
ion. A carbocation can be formed when a chemical
species breaks off from a molecule, taking the
electrons from the former single bond with it. The
chemical species formed is called the leaving group.
The bond breaks because doing so forms one or more
stable ions or molecules.
35
35
Recall (Last week): Carbocation

Rearrangements
• The product of electrophilic addition to an alkene involves
rupture of a p bond and formation of two new s bonds in its
place. In the following addition only 17% of the expected
product is formed.
• Rearrangement: A reaction in which the connectivity of atoms
in the product is different from that in the starting material.
36
36
18
Recall (Last week): Carbocation
Rearrangements
• In the rearrangements we examine, typically either
an alkyl group or a hydrogen atom migrates with its
bonding electrons from an atom to an adjacent
electron-deficient atom as illustrated in the
following mechanism. The key step in this type of
rearrangement is called a 1,2-shift.
37
37
SN1 example: The solvolysis of tert-butyl bromide

Step 1: Break a bond to form a
stable ion or molecule. Ionization of
the C-X bond gives a carbocation.
Step 2: Reaction of a nucleophile and an electrophile to form a new

covalent bond.
Step 3: Take a proton away. Proton transfer to methanol completes the

reaction.
38
38
19
SN1
• For an SN1 reaction at a stereocenter, the product is a
racemic mixture (a mixture of equal quantities of two
enantiomers).
Recall from Friday’s class
39
Recall (last week): Energy diagram for a two-step exothermic

reaction involving formation of a reaction intermediate.
Reaction intermediate: An energy minimum between two transition steps.
Intermediates are highly reactive and rarely, if ever, can one be isolated.
Rate-determining step: The step in a reaction sequence that crosses the highest energy
barrier; the slowest step in a multistep reaction.
Two-step exothermic reaction involving the formation of a reaction intermediate

40
40
20
An energy diagram for an SN1 reaction. There are
two transition states and one intermediate.
41
41
Recall (Last week): Carbocations

• A 3° carbocation is more stable than a 2°
for its formation.
• A 2° carbocation is, in turn, more stable than a 1°
for its formation.
• Methyl and 1° carbocations are so unstable that
they are never observed in solution.
42
42
21
SN1 and Carbocation Rearrangements
When an SN1 reaction occurs from a 2° haloalkane, a 2°

carbocation is formed, which is prone to rearrange to a
more stable 3° carbocation (Section 5.4).
43
43
Example
Which statements apply to an SN1 reaction?

I. The rate limiting step of the reaction involves the alkyl
halide and the nucleophile.
II. The order of reactivity is methyl > 1°> 2° > 3°.
III. The rate limiting step of the reaction involves only the
alkyl halide.
IV. There is an intermediate carbocation.
44
44
22
HALOALKANES
NUCLEOPHILIC ALIPHATIC SUBSTITUTION: SN1 AND SN2
DOMINATING FACTORS
45
45
Evidence for SN Reactions

• Let us examine some of the experimental evidence
on which these two mechanisms are based and, as
we do, consider the following questions.
• What effect does the structure of the nucleophile have
on the rate of reaction?
• What effect does the structure of the haloalkane have
• What effect does the structure of the leaving group have
• What is the role of the solvent?
46
46
23
Nucleophilicity
• Nucleophilicity: a kinetic property measured by the
rate at which a Nu: attacks a reference compound
under a standard set of experimental conditions.
• For example, the rate at which a set of nucleophiles
displaces bromide ion from bromoethane in ethanol at
25 °C.
• Table 7.2 shows common nucleophiles and their

relative nucleophilicities
47
47
Common nucleophiles and their relative

nucleophilicity
48
48
24
Effect of the Structure of the Haloalkane
• SN1 reactions
• governed by electronic factors, namely the
relative stabilities of carbocation intermediates
• relative rates: 3° > 2° > 1° > methyl
• SN2 reactions
• governed by steric factors, namely the relative
ease of approach of the nucleophile to the site of
reaction
• relative rates: methyl > 1° > 2° > 3°
49
49
Structure of the Haloalkane

• Steric factors
• Compare access to the reaction center in bromoethane
and 2-bromo-2-methylpropane (tert-butyl chloride)
50
50
25
Structure of the Haloalkane
• Effect of electronic and steric factors in competition
between SN1 and SN2 reactions of haloalkanes.
51
51
The Leaving Group

• The best leaving groups in this series are the
halogens I–, Br–, and Cl–.
• OH–, RO–, and NH2– are such poor leaving groups
that they are rarely, if ever displaced in nucleophilic
substitution reactions.
52
52
26
The Leaving Group
• Hydroxide ion, OH–, is a poor leaving group. However, the
–OH group of an alcohol can act as a leaving group, H2O, if
the –OH group is first protonated by an acid to form —
OH2+, a better leaving group.
53
53
The Solvent
• Protic solvent: a solvent that contains an –OH group
and is a hydrogen bond donor.
• these solvents favor SN1 reactions; the greater the polarity
of the solvent, the easier it is to form carbocations in it.
54
54
27
The Solvent
• Aprotic solvent: A solvent that does not contain an –OH
group and is not a hydrogen bond donor.
• Aprotic solvents favor SN2 reactions. Although the solvents at
the top of the table are polar, formation of carbocations in them
is more difficult than in protic solvents.
55
55
Evidence for SN Reactions

• The effect of
• the structure of the nucleophile on rate?
• the structure of the alkyl halide on rate?
• the structure of the leaving group on rate?
• the solvent on the reaction mechanism?
56
56
28
Summary of SN1 and SN2 Reactions of Haloalkanes
57
57
Example
Which solvents are polar protic?
I. ethanol
II. hexane
III. DMSO
IV. water
58
58
29
Example (7.5)
• Predict the product of each reaction, the mechanism, and the stereochemistry
of the product
59
59
Example
Which conditions are optimum for an SN1 reaction?
a) CH3CH2Cl + NaCN acetone
H3C
CHCl + H2O
b) CH3OH
H3C
c) CH3CH2CH2Br NaSH DMSO

+
CH3
DMSO
d) H3C CCl + NaCN
CH3
60
60
30
MSE245
Organic Materials
WB 138
February 14, 2022
Recall (Week 1): Functional Groups

they are:
classes.
1
1. Review: bonding, Lewis structures, hybridization, acid base chemistry
10. Amines (Ch 10)
11. Aldehydes and Ketones (handouts)
3
Chapter 8
• Introduction to alcohols (8.1)

• Reactions and production of alcohols (8.2)
• Ethers – brief overview (8.3)
• Thiols (8.5)
• Reactions of Thiols – brief overview (8.6)
2
ALCOHOLS, ETHERS &
THIOLS
ALCOHOLS
Alcohols - Structure
• The functional group of an alcohol is
an -OH (hydroxyl) group bonded to an
sp3 hybridized carbon.
• Bond angles about the hydroxyl oxygen
atom are approximately 109.5°.
• Oxygen is also sp3 hybridized.
• Two sp3 hybrid orbitals form sigma
bonds to carbon and hydrogen.
• The remaining two sp3 hybrid orbitals
each contain an unshared pair of
electrons.
6
3
Recall (Week 1): Alcohols - Nomenclature
• IUPAC names
• The parent chain is the longest chain that contains the
-OH group.
• Number the parent chain in the direction that gives
the -OH group the lower number.
• Change the suffix -e to -ol.
• Common names
• Name the alkyl group bonded to oxygen followed by
the word alcohol.
Examples: Naming Alcohols

OH
OH
OH
OH
OH
OH
OH
OH
OH OHOH
OHOH OH
OHOH
OH
OH
OH
OHOH
Ethanol
Ethanol 1-Propanol
1-Propanol 2-Propanol
2-Propanol
Ethanol
Ethanol
Ethanol
Ethanol
Ethanol 1-Propanol
1-Propanol
1-Propanol
1-Propanol
1-Propanol 2-Propanol
2-Propanol
2-Propanol
2-Propanol
2-Propanol
(Ethyl
(Ethylalcohol)
alcohol) (Propyl
(Propyl alcohol)
alcohol) (Isopropyl
(Isopropyl alcohol)
alcohol)
(Ethyl
(Ethyl
(Ethyl
(Ethyl
(Ethylalcohol)
alcohol)
alcohol)
alcohol)
alcohol) (Propyl
(Propyl
(Propyl
(Propyl
(Propyl alcohol)
alcohol)
alcohol)
alcohol)
alcohol) (Isopropyl
(Isopropyl
(Isopropyl
(Isopropyl
(Isopropyl alcohol)
alcohol)
alcohol)
alcohol)
alcohol)
OH
OH
OH
OH
OH
OH
OH
OH
OH OH
OH
OH
OH
OH
OH
OH OH
OHOH
OH
OH
1-Butanol
1-Butanol 2-Butanol
2-Butanol 2-Methyl-1-propanol
2-Methyl-1-propanol
1-Butanol
1-Butanol
1-Butanol
1-Butanol
1-Butanol 2-Butanol
2-Butanol 2-Methyl-1-propanol
2-Methyl-1-propanol
(Butyl
(Butyl alcohol)
alcohol) (sec-Butyl
2-Butanol
2-Butanol
2-Butanol
(sec-Butyl alcohol) 2-Methyl-1-propanol
alcohol) 2-Methyl-1-propanol
2-Methyl-1-propanol
(Isobutylalcohol)
(Isobutyl alcohol)
(Butyl
(Butyl
(Butyl
(Butyl
(Butyl alcohol)
alcohol)
alcohol)
alcohol)
alcohol) (sec-Butyl
(sec-Butyl alcohol)
alcohol)
(sec-Butyl
(sec-Butyl
(sec-Butyl
alcohol)
alcohol) (Isobutyl
alcohol) (Isobutyl
(Isobutyl
(Isobutyl
(Isobutylalcohol)
alcohol)
alcohol)
alcohol)
alcohol)
OH
OH OH
OH
OH
OH
OH
OH
OH OH
OH
OH
OH
OH
2-Methyl-2-propanol
2-Methyl-2-propanol Cyclohexanol
Cyclohexanol
2-Methyl-2-propanol
2-Methyl-2-propanol
2-Methyl-2-propanol
2-Methyl-2-propanol
2-Methyl-2-propanol Cyclohexanol
Cyclohexanol
Cyclohexanol
Cyclohexanol
Cyclohexanol
(tert-Butyl
(tert-Butylalcohol) (Cyclohexyl
(Cyclohexyl
alcohol) (Cyclohexyl alcohol)
alcohol) 8
(tert-Butyl
(tert-Butyl
(tert-Butylalcohol)
(tert-Butyl
(tert-Butyl alcohol)
alcohol) (Cyclohexyl
alcohol)
alcohol) (Cyclohexylalcohol)
(Cyclohexyl
(Cyclohexylalcohol)
alcohol)
alcohol)
alcohol)
8
4
• Write the name of each alcohol
(a) CH3 (CH 2 )6 CH2 OH
OH
(b)
OH
(c)

• Compounds containing
• two -OH groups are named as diols.
• three -OH groups are named as triols.
• Compounds containing -OH groups on different carbons
are often called glycols.
10
10
5
Unsaturated alcohols
• the double bond is shown by the infix -en-
• the hydroxyl group is shown by the suffix -ol
• number the chain to give OH the lower number
6 4 2
5 3 1 OH
trans-3-hexene-1-ol
(E)-3-hexene-1-ol
11
11
Physical Properties
• Alcohols are polar compounds
• Both the C-O and O-H bonds are polar covalent
• Partial positive charge on C and H and a partial negative
charge on O
• Alcohols associate in liquid state by hydrogen bonding
H
d+ d-
C O
H d+
H H
12
12
6
Hydrogen Bonding (review)
• Alcohols associate in the liquid state by hydrogen bonding
• Hydrogen bonding: the attractive force between a partial
positive charge on hydrogen and a partial negative charge on a
nearby oxygen, nitrogen, or fluorine atom
• the strength of hydrogen bonding in
alcohols is approximately 2 to 5
kcal/mol
• hydrogen bonds are considerably
weaker than covalent bonds (for
example, 110 kcal/mol for an O-H
bond)
• nonetheless, hydrogen bonding can
have a significant effect on physical
properties
13
13
Boiling Points
Alcohols have higher boiling points and are more soluble in water
than hydrocarbons
14
14
7
Solubility of alcohols in water
• The small alcohols are completely
soluble in water.
• In both pure water and pure ethanol the
main intermolecular attractions are
hydrogen bonds.
• In addition, there is an increase in the
disorder of the system - an increase in
entropy.
• Solubility falls as the hydrocarbon chain
in the alcohol increases.
• The -OH end of the alcohol molecules can
form new hydrogen bonds with water
molecules, but the hydrocarbon "tail"
doesn't form hydrogen bonds.
• The attractions are much weaker. Even
allowing for the increase in disorder, the
process becomes less feasible 15
15
ALCOHOLS, ETHERS &

THIOLS
REACTIONS OF ALCOHOLS
16
16
8
Acidity of Alcohols
• Most alcohols are about the same or slightly weaker
acids than water
• Aqueous solutions of alcohols have the same pH as that of

pure water
• You can treat small alcohols as water in many cases.
17
17
Acidity of Alcohols
• pKa values for several low-molecular-weight alcohols
18
9
Basicity of Alcohols
• In the presence of strong acids, the oxygen atom of an
alcohol behaves as a weak base
• Proton transfer from the strong acid forms an oxonium ion
• Thus, alcohols can function as both weak acids and weak

bases, similar to water.
19
19
Reaction with Active Metals

• Alcohols react with Li, Na, K, and other active
metals to liberate hydrogen gas and form metal
alkoxides (alkoxide functional group: RO-)
• Na is oxidized to Na+ and H+ is reduced to H2
• alkoxides are somewhat stronger bases than OH-

• alkoxides can be used as nucleophiles in nucleophilic
substitution reactions
• they can also be used as bases in b-elimination
reactions
20
20
10
Example (Review)
• Which are secondary alcohols?
CH3 H OH
CH3 H3C H
H3C C OH C C
OH H CHCH3
CH3
OH
I II III IV
21
21
Recall (last week): Formation of

haloalkanes (alkyl halides)
Most common preparation method is from reacting an
alcohol with a strong acid (hydrogen halide, HX); Chapter 8
22
22
11
Recall (Week 1): Acid and Base Strength
• Strong acid: One that reacts completely or almost
completely with water to form H3O+ ions.
• Strong base: One that reacts completely or almost
completely with water to form OH– ions.
• Here are the six most common strong acids and the
four most common strong bases.
23
23
Conversion of ROH to RX
• Water-soluble 3° alcohols react very rapidly with
HCl, HBr, and HI.
• Low-molecular-weight 1° and 2° alcohols are

unreactive under these conditions.
24
24
12
Conversion of ROH to RX
• Water-insoluble 3° alcohols react by bubbling gaseous
HCl through a solution of the alcohol dissolved in
diethyl ether or THF.
• 1° and 2° alcohols require concentrated HBr and HI to

form alkyl bromides and iodides.
25
25
Reaction of a 3° ROH with HX
• 3° Alcohols react with HX by an SN1 mechanism

• Step 1: Add a proton. Rapid and reversible proton from the acid to the —
OH group.
• This proton-transfer converts the leaving group from OH–, a poor leaving
group, to H2O, a better leaving group.
26
26
13
• Step 2: Break a bond to form a stable molecule or ion.
Loss of H2O gives a 3° carbocation.
• Step 3: Reaction of an electrophile and a nucleophile to

form a new covalent bond completes the reaction.
27

• 1° alcohols react with HX by an SN2 mechanism.
• Step 1: Add a proton. Proton transfer to OH converts OH–, a
poor leaving group, to H2O a better leaving group.
• Step 2: Reaction of a nucleophile and an electrophile to

form a new covalent bond and break a bond.
28
28
14
Reaction of ROH with HX
• Reactions are governed by a combination of
electronic and steric effects
29
29
Acid-catalyzed dehydration of alcohols
• An alcohol can be converted to an alkene by

dehydration, the elimination of H and OH from
adjacent carbons (a b-elimination)
• 1° alcohols must be heated at high temperature in the
presence of an acid catalyst, such as H2SO4 or H3PO4
• 2° alcohols undergo dehydration at somewhat lower
temperatures
• 3° alcohols often require temperatures only at or slightly
above room temperature
30
30
15
Dehydration of Alcohols
31
31
Dehydration of Alcohols
• When isomeric alkenes are obtained, the more
stable alkene (the one with the greater number of
substituents on the double bond) generally
predominates (Zaitsev’s rule).
32
32
16
Dehydration of 3° Alcohols
• Alcohols undergo dehydration - the elimination of H2O, to give alkenes.
• One of the common methods for secondary and tertiary alcohols is
treatment with a strong acid.
• Acid-catalyzed dehydrations usually follow Zaitsev’s rule and yield the
more highly substituted alkene as major products.
• It is an E1 reaction
33
33
Dehydration of a 2° Alcohol
• A three-step mechanism
• Step 1: Add a proton. Proton transfer from H3O+ to the –OH
group converts OH–, a poor leaving group, into H2O, a better
leaving group.
34
34
17
• Step 2: Break a bond to form a stable molecule or ion. Loss
of H2O gives a carbocation intermediate.
• Step 3: Take a proton away. Proton transfer from an

adjacent carbon to H2O gives the alkene and regenerates
the acid catalyst.
35
35
• A two-step mechanism
• Step 1: Add a proton. Proton transfer from the acid gives
an oxonium ion.
• Step 2: Take a proton away and loss of H2O gives the

alkene and regenerates the acid catalyst.
36
36
18
Recall: Addition of H2O to an Alkene
(Hydration)
• Acid-catalyzed hydration of an alkene is regioselective:
hydrogen adds preferentially to the less substituted
carbon of the double bond. Thus H–OH adds to alkenes
in accordance with Markovnikov's rule.
37
37
Hydration-Dehydration
• Acid-catalyzed hydration of an alkene and
dehydration of an alcohol are competing processes.
• Large amounts of water favor alcohol formation.

• Scarcity of water or experimental conditions where
water is removed favor alkene formation.
38
38
19
Oxidation of Alcohols
• One of the most valuable reaction of alcohols is their oxidation to
yield carbonyl compounds: CH-OH à C=O
• Primary alcohols yield aldehydes or carboxylic acids (Ch 13/14)
• Secondary alcohols yield ketones
• Tertiary alcohols don’t normally react with oxidizing agents
39
39
• Oxidation of a 1° alcohol gives an aldehyde or a
carboxylic acid, depending on the oxidizing agent
and experimental conditions. Oxidation of a 2°
alcohol gives a ketone.
• The most common oxidizing agent is chromic acid.
• Chromic acid oxidation of 1-octanol gives octanoic acid.
40
40
20
• To oxidize a 1° alcohol to an aldehyde, use PCC.
• PCC oxidation of geraniol gives geranial.
• Tertiary alcohols are not oxidized by either of these reagents;

they are resistant to oxidation.
41
41
Example
H2CrO4
OH acetone
H2O
42
42
21
Diols
• Diols are named systematically as poly-alcohols
• e.g. HOCH2CH2OH = 1,2-ethanediol, so the same nomenclature rules as for
alcohols apply.
• 1,2-diols are often referred to as vicinal diols.
Functional group suffix = -diol
Functional group prefix = dihydroxy-
Physical Properties:
• The polar nature of the O-H bond, suggest that diols are:
• high melting and boiling points compared to analogous alkanes
• high solubility in aqueous media
Structure:
• Basically the same as for alcohols
• Each alcohol functional group consists of an O atom bonded to a C atom
and a H atom via s bonds.
• Both the C-O and the O-H bonds are polar due to the high electronegativity
of the O atom.
Reactivity:
• In general the chemistry of diols is much the same as that of alcohols. 43
43
ALCOHOLS, ETHERS &

THIOLS
PRODUCTION OF ALCOHOLS
44
44
22
Production of Alcohols
• Alcohols can be prepared by adding water to an alkene in the presence
of a strong acid such as concentrated sulfuric acid (Ch 5). This reaction
involves adding an H2O molecule across a C=C double bond. Because
these reactions follow Markovnikov’s rule, the product of the reaction is
often a highly substituted 2° or 3° alcohol.
• Less substituted 1° alcohols can be prepared by substitution reactions

(Ch 7) that occur when a primary alkyl halide is allowed to react with
the OH- ion.
CH3CH2CH2Br + OH- à CH3CH2CH2OH + Br -
• Other methods include
• Reduction of aldehydes and ketones
• Reduction of esters
• Reduction of carboxylic acids etc… 45
45
Production of ethanol
• Ethanol is manufactured by reacting ethene with steam. The catalyst
used is solid silicon dioxide coated with phosphoric(V) acid. The
reaction is reversible.
• Only 5% of the ethene is converted into ethanol at each pass through

the reactor. By removing the ethanol from the equilibrium mixture
and recycling the ethene, it is possible to achieve an overall 95%
conversion.
46
46
23
ALCOHOLS, ETHERS &
THIOLS
ETHERS
47
47
Ethers - Structure
• The functional group of an ether is an oxygen atom
bonded to two carbon atoms (R-O-R’)
• oxygen is sp3 hybridized with bond angles of
approximately 109.5°
• in dimethyl ether, the C-O-C bond angle is 110.3°
H H
••
H C O C H
••
H H
48
48
24
Ethers - Nomenclature
• IUPAC
• The longest carbon chain is the parent alkane.
• Name the -OR group as an alkoxy (alkyl + oxygen) substituent.
• Common names:
• Name the groups bonded to oxygen followed by the word
ether.
49
49
Ethers - Nomenclature
• Although cyclic ethers have IUPAC names, their
common names are more widely used.
50
50
25
Ethers - Physical Properties
• Ethers are polar molecules.
• Each C-O bond is polar covalent.
• However, only weak attractive forces exist between ether
molecules in the pure liquid.
51
51

• The effect of hydrogen bonding is illustrated by
comparing the boiling points of ethanol and dimethyl
ether
CH 3CH2OH CH3OCH3
Ethanol Dimethyl ether
bp 78°C bp -24°C
52
52
26
Boiling points are lower than those of alcohols
53
53

Ethers are hydrogen bond acceptors only. They are not
hydrogen bond donors.
54
27
Recall: Functional Isomers
• They have the same molecular formula but differ in the nature
of the functional group.
• e.g: Dimethyl Ether: (CH3)2O and Ethanol: C2H5OH.
• Even though the atoms are the same, they are arranged differently. This
yields two different compounds with the same number of atoms. These
compounds have different functional groups. They are functional
isomers (belong to constitutional isomers).
• The first is a gas which will knock you out if inhaled. The other is
common alcohol drunk in spirits. The two molecules are shown below.
Dimethyl Ether Ethanol
55
55
Alcohols versus Ethers

• There are important differences between both the physical and
chemical properties of alcohols and ethers. Consider diethyl ether
and 1-butanol, for example, which are constitutional isomers with
the formula C4H10O.
CH3CH2OCH2CH3 CH3CH2CH2CH2OH
BP = 34.5 C BP = 117.2 C
d = 0.7138 g/mL d = 0.8098 g/mL
56
56
28
Reactions of Ethers
• Ethers resemble hydrocarbons in their resistance to
chemical reaction
• they do not react with strong oxidizing agents such as
chromic acid, H2CrO4
• they are not affected by most acids and bases at
moderate temperatures
• Because of their good solvent properties and
general inertness to chemical reaction, ethers are
excellent solvents in which to carry out organic
reactions
• But, epoxides (cyclic ether in which O is one atom
of a 3-membered ring) reacts readily because of
angle strain
57
57
Preparation of Ethers
• Ethers are easily prepared from alcohols by
conversion to the alkoxide ion by SN2 reaction.
• The substrate is a primary alkyl halide (Ch 7)
58
58
29
ALCOHOLS, ETHERS &
THIOLS
THIOLS
59
59
Thiols - Structure
• The functional group of a thiol is an -SH (sulfhydryl)
group bonded to an sp3 hybridized carbon
60
60
30
Thiols - Nomenclature
• The parent chain is the longest chain containing the -SH
group.
• Add -thiol to the name of the parent chain.
• Common names
• Name the alkyl group bonded to sulfur followed by the word
mercaptan.
• Alternatively, indicate the -SH by the prefix mercapto.
61
61
Thiols - Physical Properties

• Low-molecular-weight thiols have a STENCH
62
62
31
Thiols - Physical Properties
• The difference in electronegativity between S and
H is 2.5 – 2.1 = 0.4 (nonpolar covalent bond)
• Because of their low polarity, thiols
• show little association by hydrogen bonding.
• have lower boiling points and are less soluble in water
than alcohols of comparable MW.
63
63
Example
• Arrange the compounds in the order of increasing boiling
point (lowest first).
O
H3C CH3 H2O CH3CH2OH CH3CH2SH
I II III IV
64
64
32
ALCOHOLS, ETHERS &
THIOLS
REACTIONS OF THIOLS
65
65
Acidity of Thiols
• Thiols are stronger acids than alcohols.
• Thiols react with strong bases to form salts.
66
66
33
Oxidation of Thiols
• Thiols are oxidized by a variety of oxidizing agents,
including O2, to disulfides.
• Disulfides, in turn, are easily reduced to thiols by
several reagents.
• This easy interconversion between thiols and disulfides

is very important in protein chemistry.
67
67
Example
• Arrange the compounds in the order of increasing
acidity (least first).
68
68
34
MSE245
Organic Materials
WB 138
February 28, 2024
Recall: There are 4 classes of hydrocarbons

Hydrocarbon: A compound composed only
of carbon and hydrogen Unsaturated hydrocarbon: A
hydrocarbon that contains one or
more carbon-carbon double or
Arene: aromatic
hydrocarbon;
benzene and its
derivatives are highly
unsaturated
compounds that are
unexpectedly stable
towards reagents
that react with
alkenes
2
1
1. Review: bonding, Lewis structures, hybridization, acid base chemistry
10. Amines (Ch 10)
11. Aldehydes and Ketones (handouts)
3
Chapter 9
• Structure of benzene (9.1)

• Concept of aromacity – brief overview (9.2)
• Nomenclature (9.3)
• Reaction of benzene: oxidation at a benzylic position
(9.4)
• Reaction of benzene: electrophilic aromatic
substitution (9.5)
• Mechanism of electrophilic aromatic substitution (9.6)
• Disubstitution and polysubstitution (9.7)
• Phenols (9.8)
2
BENZENE & ITS
DERIVATIVES
STRUCTURE OF BENZENE
Benzene, C6H6, is a colorless and flammable

liquid
Benzene
Breathing very high levels of
Chemical name Benzene
benzene can result in death, while
Chemical formula C6H6
high levels can cause drowsiness,
Molecular mass 78.11 g/mol dizziness, rapid heart rate,
Density 0.8786 g/ml headaches, tremors, confusion,
Melting point 5.5 °C and unconsciousness.
Boiling point 80.1 °C
Airborne: The maximum time-
Heat of vaporization 44.3 kJ/mol weighted average (TWA) exposure
limit is 1 part of benzene vapor per
Heat of fusion 9.84 kJ/mol million parts of air (1 ppm) for an 8-
hour workday and the maximum
short-term exposure limit (STEL) is
5 ppm for any 15-minute period.
6
3
Benzene - Kekulé
• The first structure for benzene was proposed by August
Kekulé in 1872.
• This structure, however, did not account for the unusual

chemical reactivity of benzene (it did not show reactions
typical of alkenes)
7
Benzene – Orbital Overlap Model

• The concepts of hybridization of atomic orbitals and
the theory of resonance, developed in the 1930s,
provided the first adequate description of
benzene’s structure.
• The carbon skeleton is a regular hexagon, with all C-C-C
and H-C-C bond angles 120°.
C=C bond = 1.34 Å

C-C bond = 1.54 Å 8
4
Benzene - Orbital Overlap Model
The carbon framework; the six Overlap of the six 2p orbitals forms a
parallel 2p orbitals, each with continuous p cloud, shown as one
one electron, are shown torus above the plane of the ring,
uncombined. the other below it.
Benzene - Resonance Model

• Benzene is the most typical example of resonance in 2 forms.
• Benzene, with two resonance structures of equal energy is
more stable and less reactive than a typical alkene.
• We often represent benzene as a hybrid of 2 equivalent
contributing Kekulé structures.
• Each contributing structure makes an equal contribution to the
hybrid.
• The C-C bonds are neither double nor single but something in
between.
• The true structure is the intermediate of these two with 6 sp2
hybridization and 6 p bonds.
10
5
Benzene - Resonance Energy
• Resonance energy: The difference in energy between a
resonance hybrid and its most stable hypothetical contributing
structure in which electrons are localized on particular atoms
and in particular bonds.
• One way to estimate the resonance energy of benzene is to compare
the heats of hydrogenation of benzene and cyclohexene (Recall:
Chapter 5, January 31 lecture).
• Heats of hydrogenation for both cyclohexene and benzene are
negative (heat is liberated)
11
Benzene - Resonance Energy
12
12
6
BENZENE & ITS
DERIVATIVES
CONCEPT OF AROMACITY (BRIEF)
13
13
Concept of Aromaticity
• The criteria for aromaticity (whether a hydrocarbon is
aromatic/an arene or not) were recognized in the early
1930s by Erich Hückel.
• To be aromatic, a ring must:
• have one 2p orbital on each atom of the ring.
• be planar or nearly planar, so that overlap of all 2p orbitals of
the ring is continuous or nearly continuous.
• have 2, 6, 10, 14, 18, and so forth p electrons in the cyclic
arrangement of 2p orbitals (4n+2 rule).
• Benzene meets these criteria
• It is cyclic, planar, has one 2p orbital on each atom of the ring,
and has 6 p electrons (an aromatic sextet) in the cyclic
arrangement of its 2p orbitals.
14
14
7
Heterocyclic Aromatics
• Heterocyclic compound: A compound that contains
one or more atoms other than carbon in its ring.
• Heterocyclic aromatic compound: A heterocyclic
compound whose ring is aromatic.
• Pyridine and pyrimidine are heterocyclic analogs of
benzene; each is aromatic.
15
15
BENZENE & ITS

DERIVATIVES
NOMENCLATURE
16
16
8
Nomenclature (monosubstituted benzenes)
• A few monosubstituted compounds are named by using a group name as a
prefix to "benzene".
• A majority of these compounds, however, are referred to by singular names
that are unique.
17
17
Nomenclature (monosubstituted benzenes)

• Phenyl (C6H5-) and benzyl (C6H5CH2-) groups
• In molecules containing other functional groups, Ph- and Bn-
are often named as substituents
18
18
9
Nomenclature (disubstituted benzenes)
• Locate substituents by numbering or
• Use the locators ortho (1,2-), meta (1,3-),
and para (1,4-)
• Where one group imparts a special name,
name the compound as a derivative of
that molecule.
19
19
Examples
20
20
10
Nomenclature (polysubstituted benzenes)
• Must use numbers
• If there are three or more substituents, number the atoms
of the ring.
• If one group imparts a special name, it becomes the
parent name.
• If no group imparts a special name, number to give the
smallest set of numbers, and list alphabetically.
21
21
Examples
22
22
11
BENZENE & ITS
DERIVATIVES
REACTIONS OF BENZENE: OXIDATION AT A BENZYLIC POSITION
23
23
Reactivity of Cyclohexene and Benzene
24
24
12
Benzylic Oxidation
• Benzylic carbon: an sp3 hybridized carbon bonded to a
benzene ring
• Benzene is unaffected by strong oxidizing agents such
as H2CrO4 and KMnO4.
• Halogen and nitro substituents are unaffected by these
reagents.
• An alkyl group with at least one hydrogen on the benzylic
carbon (position next to the benzene ring) is oxidized to a
carboxyl group (-COOH).
25
Benzylic Oxidation
• If there is more than one alkyl group, each is oxidized to a -COOH
group.
• Terephthalic acid is one of the two monomers required for the

synthesis of poly(ethylene terephthalate), PETE, a polymer that
can be fabricated into Dacron polyester fibers and into Mylar
films.
26
13
BENZENE & ITS
DERIVATIVES
REACTIONS OF BENZENE: ELECTROPHILIC AROMATIC
SUBSTITUTION
27
27
Electrophilic Aromatic Substitution

• The most common reaction of aromatic compounds is electrophilic
aromatic substitution (EAS). An electron poor reagent (electrophile,
E+) reacts with the electron-rich aromatic ring (nucleophile) and
substitutes for one of the H atoms on an aromatic ring.
H E
+ +
+ E + H
• We study:
• several common types of electrophiles
• how each is generated
• the mechanism by which it replaces hydrogen
28
28
14
Some Electrophilic Aromatic Substitution Reactions
29
29
Reactions of Benzene
• The most characteristic reaction of aromatic
compounds is substitution at a ring carbon.
Chlorination/Halogenation
Nitration
30
15
Reactions of Benzene
Sulfonation
Alkylation
Acylation
31
BENZENE & ITS

DERIVATIVES
REACTIONS OF BENZENE: MECHANISM OF ELECTROPHILIC
AROMATIC SUBSTITUTION
32
32
16
Mechanism of Electrophilic Aromatic
Substitution (EAS)
All occur by a common three-step mechanism:
Step 1: Generation of the electrophile
+
Reagent(s) E
Step 2: Reaction of the electrophile with the ring

H H H H
+ slow
+ E E E E
Resonance-stabilized cation intermediate
Step 3: Proton transfer to regenerate the aromatic ring

H E
fast + Base-H
E + Base
33
33
Recall (Chapter 5): Addition of Cl2 and Br2

(Bromination, halogenation)
• Addition is stereoselective.
• Stereoselective reaction: A reaction in which one
stereoisomer is formed or destroyed in preference to all
others that might be formed or destroyed.
• Addition to a cycloalkene, for example, gives only a trans
product. The reaction occurs with anti stereoselectivity.
34
34
17
Recall (Chapter 5): Mechanism of
electrophilic addition of Cl2 and Br2
• Step 1: Reaction of a nucleophile and an electrophile to form a new covalent
bond. Reaction of the p bond (a nucleophile) with bromine (an electrophile) gives a
bridged bromonium ion intermediate
• Step 2: Reaction of a nucleophile, and an electrophile to form a new covalent

bond. Attack of bromide ion from the side opposite the bridged bromonium ion
opens the three-membered ring.
35
35
Mechanism of Electrophilic Aromatic

Substitution (EAS)
• An electrophilic aromatic substitution reaction begins in a
similar way as an alkene electrophilic addition reaction.
However with following differences:
• Aromatic rings are less
reactive toward
electrophiles.
• The way electrophile
was formed, and
• A base removes H+ from
the E bearing carbon to
yield the neutral
aromatic product to
keep the stability of the
ring structure.
36
36
18
A: Chlorination and Bromination
(Halogenation)
• Step 1: Formation of the electrophile (a chloronium ion).
• Step 2: Reaction of an electrophile and a nucleophile to form a new

covalent bond.
37
37
A: Chlorination and Bromination

(Halogenation)
• Step 3: Take a proton away. Proton transfer to FeCl4– forms HCl,

regenerates the Lewis acid catalyst, and gives chlorobenzene.
38
38
19
B: Nitration
• The electrophile, NO2+, is generated in two steps.
• Step 1: Add a proton.
• Step 2: Break a bond to form a stable molecule or ion.
39
C: Friedel-Crafts Alkylation
• Friedel-Crafts alkylation forms a new C-C bond

between an aromatic ring and an alkyl group.
40
40
20
• Step 1: Formation of an electrophile.
• Step 2: Reaction of an electrophile and a nucleophile to form

a new covalent bond.
41
41
• Step 3: Take a proton away. Proton transfer regenerates the

aromatic ring.
42
42
21
Friedel-Crafts Alkylations
• There are two major limitations on F-C alkylations.
• It is practical only with stable carbocations, such as 2° and
3° carbocations.
• It fails on benzene rings bearing one or more of these
strongly electron-withdrawing groups.
43
43
BENZENE & ITS

DERIVATIVES
DISUBSTITUTION & POLYSUBSTITUTION
44
44
22
Di- and Polysubstitution
• Existing groups on a benzene ring influence further
substitution in both orientation and rate. The 3 (o-,
m-, p-) are usually not formed together.
• Orientation
• Certain substituents direct new substitution
preferentially toward ortho-para positions, others direct
preferentially toward meta positions.
• Rate
• Certain substituents are activating toward further
substitution, others are deactivating toward further
substitution.
45
Existing substituent groups impacts

further substitution
• Ortho-para directing
• Any substituent on a benzene ring that directs electrophilic aromatic
substitution preferentially to ortho and para positions
• Meta directing
• Any substituent on a benzene ring that directs electrophilic aromatic
substitution preferentially to meta position
• Activating group
• Any substituent on a benzene ring that causes the rate of
electrophilic aromatic substitution to be greater than that for
benzene
• Deactivating group
• Any substituent on a benzene ring that causes the rate of
electrophilic aromatic substitution to be lower than that for benzene
46
46
23
—OCH3 is ortho-para directing.
—NO2 is meta directing.
47
Substituent Effects in Electrophilic Aromatic

Substitution
• Substituents affect the orientation of the reactions
• The nature of the substituent already present on the ring determines the
position of the second substitution
• The substituents can be classified into 3 groups: (1) meta-directing
deactivators, (2) ortho- and para-directing activators, and (3) halogens in
between as ortho- and para-directing deactivators.
48
48
24
49
• Generalizations
1. alkyl groups, phenyl groups, and substituents in which the
atom bonded to the ring has an unshared pair of electrons
are ortho-para directing; all other substituents are meta
directing
2. all ortho-para directing groups are activating toward further
substitution; the exception are the halogens, which are
weakly deactivating
3. all meta directing groups carry either a partial or full positive
charge on the atom bonded to the ring
Also:
• Inductive Effect
• Resonance Effect
50
50
25
Example
51
51

• The order of steps is important.
52
26
Theory of Directing Effects
• Rate of electrophilic aromatic substitution (EAS)
• EAS rate determined by the slowest step in the reaction
• For almost every EAS, the rate-determining step is attacking of
E+ on the aromatic ring to give a resonance-stabilized cation
intermediate
• The more stable this cation intermediate, the faster the rate-
determining step and the faster the overall reaction
• For ortho-para directors, ortho-para attack forms a more
stable cation than meta attack
• Ortho-para products are formed faster than meta products
• For meta directors, meta attack forms a more stable
cation than ortho-para attack
• Meta products are formed faster than ortho-para products53
53
Ortho- and Para Directors

• In general, any substituent that has a lone pair of
electrons on the atom directly bonded to the aromatic
ring allows an electron-donating resonance interaction
and is an ortho and para-director.
54
54
27
Meta Directors
• In general, any substituent that has a positively polarized atom (d+)
directly attached to the ring makes one of the resonance forms of
the ortho and para intermediates unfavorable and thus acts as a
meta director.
• In order to avoid putting the charge that develops (after attacking
an electrophile) on the carbon attached to the electron-
withdrawing group, the incoming electrophile must attach to the
meta carbons
55
55
Ortho- and Para Directors (Alkyl group)
• Alkyl groups are also ortho- and para- directors.

• Alkyl groups work somewhat differently. They are not
as strong at activating the ring, and their main
function is stabilizing the positive charge formed
after the attack on the electrophile:
56
56
28
Theory of Directing Effects – Ortho-para
Directors
For —OCH3; assume para (or ortho) attack.
OCH 3
slow
+ N O2 +
For —OCH3; assume meta attack.
OCH 3 OCH 3 OCH 3 OCH 3 OCH 3
+ + fast
slow H H H - H+
+ N O2 +
N O2
N O2 N O2 + N O2
OCH 3 OCH 3 (a) OCH 3 (b) OCH 3
(c)
57 + + fast
H H H - H+
N O2
N O2 N O2 + N O2
(a) (b) (c)
Theory of Directing Effects - Meta

Directors
For NO2; assume meta attack.
For NO2; assume para attack.
Contributor (e) places positive charge on adjacent atoms.

58
29
Halogens
• The halogens are in a class by themselves, and behave in an
unusual manner. They are VERY electron withdrawing, and
thus DEACTIVATE the ring towards electrophilic substitution
(inductively unfavored).
• However, their multiple lone-pairs are able to stabilize the
cation formed after electrophilic addition (resonantly favored),
and thus direct ortho-para.
H + H
+ E+
: :
: :
: Cl :Cl + :Cl
E E
:
59
59
Halogens
• Halogens: the resonance and inductive effects operate in
opposite directions.
• The inductive effect: the halogens are more electronegative
than carbon and have an electron-withdrawing inductive effect;
therefore, aryl halides react more slowly in EAS than benzene.
• The resonance effect: a halogen ortho- or para- to the site of
electrophilic attack stabilizes the cation intermediate by
delocalizing the positive charge; halogen, therefore, is ortho-
para directing.
60
30
Activating-Deactivating Effects
• Any resonance effect such as those of -NH2, –OH, and –OR, which delocalizes the
positive charge on the cation intermediate, lowers the activation energy for its
formation and activates the ring toward further EAS.
• Any resonance or inductive effect such as those of –NO2, –C=O, -SO3H, –NR3+, –
CCl3, and –CF3, which decreases electron density on the ring, deactivates the ring
toward further EAS.
• Any inductive effect such as –CH3 which releases electron density toward the ring
activates the ring toward further EAS.
61
Activating-Deactivating Effects
• The common characteristic of all activating groups is that they donate
electrons to the ring (i.e. making ring more electron-rich), stabilizing the
carbocation intermediate and lower the activation energy of formation.
• The common characteristic of all deactivating groups is that they
withdraw electrons from the ring (inductive effect), making the ring
electron-poor, destabilize and raise the activation energy for its formation.
• These effects are due to electronegativity (inductive effect) or resonance.
62
62
31
Examples
63
63
BENZENE & ITS

DERIVATIVES
PHENOLS
64
64
32
Phenols
• The functional group of a phenol is an -OH group
bonded to a benzene ring.
65
65
Phenols
• Some phenols
66
33
Acidity of Phenols
• Phenols are significantly more acidic than alcohols.
67
Acidity of Phenols
The greater acidity of phenols compared with alcohols is the
result of the greater stability of a phenoxide ion relative to an
alkoxide ion.
68
34
Acidity of Phenols
Ring substituents, particularly halogens and nitro groups, increase
the acidity of phenols by a combination of resonance and
inductive effects.
69
Acidity of Phenols
• Phenols are weak acids.
• They react with strong bases to form water-soluble salts.
• They do not react with weak bases, such as sodium

bicarbonate.
70
35
Acidity of Phenols
• Separations
71
36

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MSE245

January 10, 2024

Instructor (Lab): Prof. Kai Huang

Lab TA: Mr. Raunaq Bagchi

Tutorial TA: Mr. Sam Penner

• 2 lectures per week (3 hours total)

Organic Materials Chemistry

This is a custom textbook, only

• If there are any outstanding questions not answered during

CREATION AND INVENTION OF NEW MATERIALS WITH

A major category of materials is organic materials, compounds containing

• Many of these compounds are of immense importance:

MSE 245 – Organic Materials Chemistry & Processing

MSE 398 – Materials MSE 316 –

MSE 415 – Environmental MSE 401 – Materials Selection in

LEARNING A NEW FIELD IS LIKE LEARNING A NEW LANGUAGE

Need to start from the beginning (e.g., language)

• Carbon Atoms, Electrons and Orbitals

Rule 1: Orbitals fill in order of increasing energy from lowest to highest

The carbonate ion as a hybrid of three equivalent contributing

• In using curved arrows, there are only two allowed

• A p orbital consists of two

In forming the covalent bond in H–H, there is overlap of

Single bond Double bond Triple bond

s bonds are stronger than p bonds

• Notice that in an sp hybridized atom there are two unhybridized p orbitals in

• Weak base: A substance that only partially

Water Hydrogen chloride

• When HCl dissolves in water, for example, the strongest

• When HCl dissolves in methanol, the strongest available

January 17, 2024

MSE 245 Course Outline

Naming of Organic Compounds

This is an organization which regulates various

Cracking the code

The IUPAC Nomenclature

IUPAC- A General System

Nature of Carbon-Carbon Suffix Class

Names of Straight-Chain Alkanes

Alkane with branched chains

• Write the structural formula for 3-ethyl-2-methylhexane.

Recall: Unsaturated Hydrocarbons

Benzene and Phenyl Groups

IUPAC Names for Alkenes (CnH2n)

• Number and name the following:

IUPAC Names for Cycloalkenes

Alcohols – IUPAC Nomenclature

IUPAC- A General System

IUPAC - a general system

January 24, 2024

MSE 245 Course Outline

• Hydrocarbons which do not contain a benzene ring are called

Recall (from Week 1)

Alkanes have the general formula CnH2n+2

• The lowest energy (most stable) conformation of an

• An equatorial bond extends from the ring roughly

Example: Cis-trans isomerism

Boiling point and Melting point

Physical Properties of Alkanes

• Long, straight chains

Example: Burning of Long chain Carbon (Fat)

Cracking is a process whereby a larger saturated

Petroleum and Natural Gas

Crude Oil Distillation