Chapter 4 Lecture Slides PDF

Chapter 4: Alkanes and Cycloalkanes
Hello
1
Chapter 4: Alkanes and Cycloalkanes
Topics:
• Introduction to Alkanes
• Nomenclature of Alkanes
• Constitutional Isomers of Alkanes
• Relative Stability of Isomeric Alkanes
•
Hello
Sources and Uses of Alkanes
• Drawing Newman Projections
• Conformational Analysis of Ethane and Propane
• Conformational Analysis of Butane
• Cycloalkanes
• Conformations of Cyclohexane
• Drawing Chair Conformations
• Monosubstituted Cyclohexane
• Disubstituted Cyclohexane
• cis-trans Stereoisomerism
• Polycyclic Systems
2
Introduction to Alkanes
• Hydrocarbons –composed of hydrogen and carbon
Hello
Ethene Ethyne
• Hydrocarbons are saturated or unsaturated
• Saturated hydrocarbons: Contain no 𝛑 bonds, called alkanes.
• Unsaturated hydrocarbons: Contain a double bond, alkenes,

or triple bonds, alkynes.
3
Introduction to Alkanes
propane 1-propene 1-propyne

Hello
• Hydrocarbons are saturated or unsaturated
• Saturated hydrocarbons: Contain no 𝛑 bonds, called alkanes.
• Unsaturated hydrocarbons: Contain a double bond, alkenes,

or triple bonds, alkynes.
4
Nomenclature of Alkanes
• Many organic compounds have “common” names
Hello
• Common names became way too complicated as more and more
molecules kept getting discovered
• A systematic method to naming was developed for simplicity.

5
IUPAC
• The IUPAC system (pronounced “I-‐YOU-‐PACK”)

• systematic method for naming compounds
Hello
• IUPAC name includes:
– Parent name (longest carbon chain)

– Names of substituents (anything attached to the longest
carbon chain)
– Location of substituents
6
Finding the Parent Chain
1. Identify the parent chain -‐ the longest consecutive chain of carbons
Hello
7
Hello
8
oct PDUBOF tetracont UFUSBDP
non OPOBOF pentacont QFOUBD
Nomenclature
dec
of Alkanes, Finding
EFDBOF
the hect
Parent Chain
IFDUBO

re is a competition between
• If there is more two chains
than one pof equal plength,
ossible arent cthen
hain, choose
choose the chai
the
mber of substituents.
one with Substituents are branchesattached
the most substituents connected to the parent chain:
Hello
Correct Incorrect
(3 substituents) (2 substituents)
erm “cyclo” is used toBranches

• Substituent: indicate othe presence
r atoms of a ringto inthe
connected theparent
structure of an a
chain.
hese compounds are called cycloalkanes:
9
Nomenclature of Alkanes, Naming the Parent Chain
Hello
Memorize 1 -‐ 12

You will see these for the next two semesters!
10
Nomenclature of Alkanes, Finding the Parent Chain

1. Identify the parent chain -‐ the longest consecutive chain of
carbons
• If the parent chain is cyclic, add the prefix “cyclo”
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11
Identify the parent in the following compound
Hello
Answer
2 4
1 3
Hello 2 1
Incorrect Correct
2 Substituents 4 Substituents
Both parent chains are 10 carbons long so we cant choose a parent

chain based off of number of carbons. Instead we need to choose the
chain with the greatest number of substituents. In both cases the
parent is named decane.
Identify and name the parent chain in the following compounds
a. b. c.
Hello
d. e. f.
g. h. i.
Answers
a. b. c.
hexane heptane heptane
Hello
d. e. f.
nonane octane cyclopentane
g.
heptane h. i.
Three heptane parents were possible, cycloheptane cyclopropane
but this one had the most subsKtuents.
Identify the two compounds below that have the same parent chain.
Hello
a. b.
c. d.
Answer: b and c have the same parent chain; both octane.
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a. b.
heptane octane
c. d.
nonane octane
Nomenclature of Alkanes, Naming Substituents
2. Identify and name the substituents
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Memorize these (1-‐4 are the most common)

You will see these for the next two s18emesters!
Hello
Substituents end in yl instead of ane.
Memorize these (1-‐4 are the most common)

You will see these for the next two s19emesters!
The following compound is found in the urine of male mice and is
believed to play a role both in attracting females and inducing
aggression toward other males.
1. Name the parent cHello

hain.
2. Identify all groups that would be considered substituents.
3. Name each substituent.
Answers: Black/Bold = parent Red/Not bold = substituent
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ethyl
methyl
methyl
Parent = octane
1. Name the parent chain.
Hello
a. b.
c.
methyl methyl
methyl propyl
a. Hello b.
ethyl
methyl ethyl Parent = nonane
Parent = nonane
ethyl methyl
methyl
c. ethyl
methyl Parent = undecane

Nomenclature of Alkanes, Identifying Substituents

A ring can be either a parent chain or a substituent depending on the
number of carbons
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24

– For substituents with complex branches
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1. Number the longest carbon chain WITHIN the substituent. Start with
the carbon attached to the parent chain
2. Name the substituent (in this case butyl)
3. Name and Number the substituent’s side group (in this case 2-‐
methyl)
The name of the substituent is (2-‐methylbutyl)
25
Hello
Parent = decane
methyl
Hello
1.
2.
1-‐methylpropyl 3.

– Some branched substituents have common names
– Two types of propyl groups
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Memorize these
You will see these for the 28next two semesters!

– Three types of butyl groups
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Memorize these (t-‐Bu is very very common)

You will see these for the next two semesters!
29

– Three types of many types of pentyl groups
– The most common ones are listed below:
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pentyl isopentyl (or isoamyl) neopentyl

n ames:
Recommended (3-‐methylbutyl) (2,2-‐dimethylpropyl)
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a. b.
c. d.
1-‐methylethyl
1,1-‐dimethylethyl 2. or
1. isopropyl
2. or
1. tert-‐butyl
a. Hello b. methyl
Parent = heptane Parent = nonane
2,2-‐dimethylpropyl 1-‐methylethyl
or 2. or
neopentyl 1. isopropyl
1. 2. 3.
1-‐methylpropyl 1.
3. 2.
or
c. sec-‐butyl d.
Parent = nonane Parent = undecane

• Carbons in the parent chain have to be numbered.
Hello
• 2-‐methylpentane means there is a methyl group on carbon #2 of
the pentane chain
• 3-‐methylpentane means there is a methyl group on carbon #3 of
the pentane chain
33
• Guidelines to follow when numbering the parent chain
1. If ONE substituent is present, number the parent chain so that
the substituent has the lowest number possible
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34
2. When multiple substituents are present, number the parent

chain to give the first substituent the lowest number possible
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35
3. If there is a tie, then number the parent chain so that the
second substituent(locant) gets the lowest number possible
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Locant: number of a carbon atom to which another atom is bonded
36
4. If there is no other tie-‐breaker, then assign the lowest number
alphabetically
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37
– The same rules apply for cycloalkanes

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38
To assemble the complete name:
1. Put the # and name of each substituent before the parent
chain name, in alphabetical order
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5. A prefix is used (di, tri, tetra, penta, etc.) if multiple
substituents are identical.
note: “di” or “tri” is ignored when alphabetizing the

substituents
39
1. Identify the parent chain

Hello
3. Number the parent chain; assign a locant to each substituent
4. List the numbered substituents before the parent name in

alphabetical order
40
Provide a systematic name for each of the following compounds
Hello
b. c.
a.
d. e. f.
Answers
methyl methyl sec-‐butyl
8
7
methyl methyl 6
2 4 5
1 3
4
3 methyl
5 6
7 8 Hello 1
2
ethyl b. c.
a.
4-‐ethyl-‐2,3-‐dimethyloctane 3,4,6-‐trimethyloctane sec-‐butylcyclohexane
isopropyl
6 7
5
4
methyl 3
1
2 4 2
1 3 5
2
ethyl 6 5
4
3
1
d. e. f.
3-‐ethyl-‐2-‐methyl-‐heptane 3-‐ethyl-‐2,2-‐dimethylhexane
3-‐isopropyl-‐2,4-‐dimethylpentane
Provide a systematic name for each of the following compounds
Hello
a. b. c.
d. e. f.
Answers 3-‐ethyl-‐2,5-‐dimethyl-‐4-‐propylheptane
7
5 6
2
1 3
3 4
4 5 7 9
5 3 1 6 8
7 6 4 2
8
Hello 2
1
a. b. c.
2-‐cyclohexyl-‐4-‐ethyl-‐5,6-‐dimethyloctane 2,2,6,6,7,7-‐hexamethylnonane
1
5 4 2 7
1 3 6
2
3 5 3 4 5
1 2 4 6 7
d. e. f.
4-‐tert-‐butylheptane 1,3-‐diisopropylcyclopentane 3-‐ethyl-‐2,5-‐dimethylhepane

• Bicyclic compound contains two fused rings.
Hello
• To name a bicyclic compound, include the prefix bicyclo in front of
the parent name
45
Specifically, it must indicate the way in which the rings are c
must identify the two bridgeheads, which are the two carb
Nomenclature of Alkanes (Bicyclic Compounds)
together:
• The two carbons where the rings are fused Bridgehead
are bridgehead carbons
• There are three “paths” connecting the Bridgehead

Hello
bridgeheads. Count the number of carbons
in There
each pare
ath three different
to name paths connecting these two bridgehea
the compound
1
of carbon atoms, excluding the
bridgeheads themselves. In the
1
carbon atoms, another2 path has two carbon atoms, and the thir
1 1 1
atom. These three numbers,
3
ordered from largest to smallest, [2
1 2 2
of the parent, surrounded by brackets:
• Name it so the largest number is listed first Bicyclo[2.2.1]heptane
in the brackets.
These numbers provide the 46necessary specificity to differentiate
Constitutional Isomers of Alkanes
• ISOMERS
– different structures, same molecular formula
• CONSTITUTIONAL ISOMERS
Hello
– different connectivity of atoms
Structural Formula:
Molecular Formula: C6H14 C6H14
Condensed Structure: CH3CH2CH2CH2CH3 CH(CH3)2CH2CH2CH3
IUPAC Name: hexane 2-methylpentane

47
• As the number of carbon

atoms increases, the
number of constitutional
isomers increases
Hello
48
• When drawing isomers be on the lookout for identical compounds!!
• 1. Twist/rotate the molecule and the bonds (in your mind) until
you realize two compounds are the same
• 2. Name the compounds. If they have the same name, they are
the same compound. Hello
Which of the compounds below are identical?
3-‐methylpentane 2-‐methylpentane
3-‐methylpentane
2-‐methylpentane
49
• Be able to recognize different structures as either being isomers,

or being the same compound.
Hello
• You can test if structures are the same in two ways:
1. Flip one of the molecules in 3D space and rotate around its
single bonds until it is super-‐imposable on the other molecule
2. Name them. If they have the same IUPAC name, they are the
same compound
50
There are five constitutional isomers possible for a compound with
the molecular formula of C6H14. Draw and name each isomer.
Hello
Answers. If you got more than 5, two of them are the same!
hexane
Hello
2-‐methylpentane 3-‐methylpentane
2,2-‐dimethylbutane 2,3-‐dimethylbutane
For each pair of compounds, identify whether they are constitutional
isomers or two representations of the same compound.
a. b.
Hello
c. d.
Answers:
same compound same compound
a. b.
Hello
both named: 2,3-‐diemthylpentane both named: 3-‐ethyl-‐2,4-‐dimethlpentane
same compound consKtuKonal isomers
c. d.
3-‐methyl-‐4-‐propylheptane
both named: 4-‐isobutyl-‐2,8-‐dimethlnonane 2-‐methly-‐4-‐propylheptane
Relative Stability of Isomeric Alkanes
+ 12.5 O2 8CO2 + 9H2O
A ∆H = −5470 kJ/mol
+Hello
12.5 O 2 8CO2 + 9H2O
B ∆H = −5452 kJ/mol
Which reactant has more potential energy?
Which reactant has stronger bonds?
Which reactant is the least stable?

+ 12.5 O2 8CO2 + 9H2O
A ∆H = −5470 kJ/mol
Hello
+ 12.5 O 2 8CO2 + 9H2O
B ∆H = −5452 kJ/mol
Which reactant has more potential energy?

A (more heat released when burned)
Which reactant has stronger bonds?
B (lower potential energy = stronger bonds)
Which reactant is the least stable?
A (higher potential energy = weaker bonds)
Branched alkanes are more stable than linear alkanes 56

• Relative stability of isomers can be determined by measuring

heat of combustion
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57
• various components of petroleum are separated by distillation
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• The gasoline fraction of crude oil only makes up about 19%, which
is not enough to meet demand
58
• Gasoline is a mixture of straight, branched, and aromatic

hydrocarbons (5-‐12 carbons in size, branched is preferred)
• Large alkanes can be broken down into smaller molecules by
Cracking
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• Straight chain alkanes can be converted into branched alkanes

and aromatic compounds through Reforming
• After using these processes, the yield of gasoline is about 47%
rather than 19%
59
• Diesel fuel is a mixture of straight, branched hydrocarbons (12-‐20

carbons in size, straight chains are preferred
+ 12.5 O2 8CO2 + 9H2O
∆H = −5470 kJ/mol
A (higher PE) Hello
+ 12.5 O2 8CO2 + 9H2O
∆H = −5452 kJ/mol
B (Lower PE)
Diesel, fuels, which are primarily straight chained alkanes have a lower
activation energy, so compression is enough to ignite them, no spark plug
is necessary.
Gasoline, has a higher activation energy, spark plugs are needed to begin
ignition inside your car engine. Don’t confuse this with volatility, gasoline
molecules are smaller, evaporate more quickly and will burn faster. 60
Drawing Newman Projections
• Single bonds rotate, resulting in multiple 3-‐D shapes, called

conformations
• It is important that we can clearly see these 3-‐D conformations.
• Some are higher
Hello in energy then others.
• Some will react and others will not.
• We will have to worry about for both semesters of O-‐Chem
61
• There are various ways to represent the 3-‐D shape of a compound
• The three projections below are similar, from left to right, slowly
rotate the molecule so the red H’s are turned toward you.
Hello
• Newman projections are ideal for comparing the relative stability

of possible conformations resulting from single bond rotation
62
• A Newman projection is the perspective of looking straight down

a particular C-‐C bond
• Show the front carbon as a point and the back carbon as a large
circle behind it. Hello
Cl
63
Newman Projections
For each case below, draw a Newman projection as viewed from the
angle indicated.
Cl
Cl
a.
Hello c.
b.
Cl Cl
Cl Cl
Cl Br
d. e. f.
If you are struggling with this, make a model at home, and use that to help you out!
Answers: These can be tricky. You really need to practice visualizing the
molecule. Dash is in, wedge is out, and try to rotate the molecule so you
are looking down the desired C-‐C bond. Me = methyl = CH3
Et = ethyl = CH3CH2
Cl
Cl
a. Hello b.
Nohce the Cl’s and Me’s
c.
Me Me Et
Me Me H Cl are opposite of one H Me
another, make sure that is
H H Cl H the case in the Newman H H
Me Me Et
Projechon as well!
Cl Cl
Cl Cl
Cl Br Me
d. e. f. H Cl
Me
Nohce the Cl’s are on the same
Br H
Cl side, the Me’s are opposite.
Me
H Me
Cl Cl
Make sure what you see in the
H H H Cl structure also makes it to the Halogens and Me’s
Me Me
Newman Projechon are opposite
Conformational Analysis of Ethane and Propane
• The angle between atoms on adjacent carbons is called a dihedral
angle or torsional angle. It is 60° in the molecule below
Hello
66
• Staggered conformations(dihedral angels are 60°) are more

stable (lower in energy) than eclipsed conformations (dihedral
angles are 0°)
Hello
• The difference in energy between these conformations is due to
torsional strain. Here, the difference in energy is 12 kJ/mol
67
Conformational Analysis of Ethane
For Ethane
All eclipsed
conformations are
degenerate
Hello
All staggered
conformations are
degenerate
68
• One theory is that the eclipsed conformation is 12 kJ/mol less
stable because of electron pair repulsion between the eclipsing
bonds (4 kJ/mol for each eclipsing interaction)
Hello
• With a difference of 12 kJ/mol in stability, at room temperature,
99% of the molecules will be in the staggered conformation
69
• The difference in energy can also be rationalized by the presence
of stabilizing interactions in the staggered conformation
Hello
• A filled, bonding MO has

side-‐on-‐side overlap with
an empty anti-‐bonding
MO.
There has been debate for years about this, but recent
calculations support this as the more accurate model 70
Conformational Analysis of Propane
For Propane
• The analysis of torsional strain for propane (below) is similar to
ethane
Hello
71
Conformational Analysis of Propane
• The barrier to rotation for propane is 14 kJ/mol, which is 2 kJ/mol
more than for ethane
• If each H-‐-‐-‐-‐-‐H eclipsing interaction costs 4 kJ/mol of stability, that

total can be subtracted Hello from the total 14 kJ/mol to calculate the
contribution of a CH3-‐-‐-‐-‐-‐H eclipsing interaction
72
Conformational Analysis of Butane
• The analysis of torsional strain for butane shows more variation
• Note that there are multiple staggered conformations and
multiple eclipsed conformations
All eclipsed
conformations are
NOT degenerate Hello
All staggered
conformations are
NOT degenerate
73
• The stability of the different staggered conformations differs by

3.8 kJ/mol
• When the methyl groups are gauche to one another, there is
steric strain, and a higher energy conformation than when they
are anti to one another.
Hello Called a gauche interaction.
We will be making models in lab. Prove it to yourself! 74
Hello
75
Hello
76
• The highest energy conformation for butane results when the

methyl groups eclipse one another
Hello
• Each CH3-‐-‐-‐-‐-‐CH3 eclipsing interaction accounts for 11 kJ/mol of

energy (torsional and steric strain).
• The barrier for rotation around the C2 and C3 bond is around 19 kJ/
mol
77
• The energy costs for eclipsing and gauche interactions can be used
to approximate the energy of a given conformation
Hello
78
Consider the following compound:
a. Rotating only the C3—C4 bond, identify the lowest energy Newman
conformation. Hello
b. Rotating only the C3—C4 bond, identify the highest energy Newman
conformation.
2 3 4 5 6
Conformational Analysis of Butane 1
Answers (a). The lowest energy conformations are the staggered

conformations. In this case you want the largest groups (the ethyl
groups) as far apart as possible (anti). C1—C2 = Ethyl C5—C6 = Ethyl
Et Et Et
Et Et
H Me H
Hello
Me H Me
Et
Lowest Energy
Answers (b). The highest energy conformations are the eclipsed

conformations. In this case, the highest energy eclipsed conformation
results when the two ethyl groups are eclipsing each other.
Et Et Et Et
Et
H Me H Me H Me
Et
Highest Energy
Cycloalkanes
• Ideal bond angles for sp3 hybridized carbon is 109.5˚

• Which of these rings do you think exist?
Hello
81
Cycloalkanes
• Ideal bond angles for sp3 hybridized carbon is 109.5˚

• If cycloalkanes were flat, each carbon in the ring would
experience angle strain.
Hello
• Also, if a ring was flat, then all the C-‐C bonds would be in eclipsing
rotamers… causing considerable torsional strain.
82
Cycloalkanes
• The combustion data for cycloalkanes shows that a 6-‐member

ring is the most most stable ring size (it is lowest in energy per
CH2 group)
Hello
83
Cycloalkanes
Cyclopropane
• What is the hybridization of each carbon atom?

• sp3 Hello
• What is ideal bond angle for a carbon that is sp3
hybridized?
• 109.5°
• What is the bond angle for cyclopropane?
• 60°
• Do you think this is a very stable molecule?
• NO!
84
Cycloalkanes
Cyclopropane
• Cyclopropane has Hello

severe angle strain (60°)!
• The obtains still point out a 109.5°, however, they
do not overlap well with one another.
• Banana Bonds!
HH
• Cyclopropane also has significant torsional strain since C H
all the hydrogens are eclipsed. HH C
• Cyclopropane has the highest potential energy of all the

rings and reacts readily!
85
Cycloalkanes
• Cyclobutane is 27 kJ/mol less stable than cyclohexane per CH2
group.
1. Angle strain bond angles of 88°
2. Slight torsional strain results because adjacent C-‐H bonds are
Hello
neither fully eclipsed nor fully staggered
Puckered conformation has less torsional strain than a flat

conformation
86
Cycloalkanes
• Cyclopentane is only 5 kJ/mol less stable than cyclohexane per

CH2 group
1. Very little angle strain -‐ bond angles are nearly 109.5˚
2. Slight torsional strain – adopts an envelope conformation to
Hello
avoid most of it
H
H H
H
H
H
H
H H H
87
Cyclohexane
• Cyclohexane can adopt a variety of conformations, but it is the
chair conformation that is the most stable
Hello
• The chair and boat conformations are the most common.

88
Cyclohexane
• Cyclohexane has no ring strain in a chair conformation
1. No angle strain – beyond angles are 109.5°

2. No torsional Hello
strain -‐ all adjacent C-‐H bonds are staggered
The other possible conformations of cyclohexane have some

amount of angle and/or torsional strain (i.e. ring strain)
89
Cyclohexane
• Cyclohexane also has no ring strain in the boat conformation
however…
Flagpole Interactions
Hello H H
• Flagpole interactions are a form of transannular strain (also

called Prelog strain after the Nobel Laureate Vladimir Prelog)
which is the are unfavorable interaction of ring subsitutents on
non-‐adjacent carbons. We call this steric hinderance.
90
Drawing Chair Conformations: The sooner you learn
this, the better!
• Drawing a chair conformation for cyclohexane
Hello
91
this, the better!
• If drawn correctly, the chair should contain 3 sets of parallel lines
Hello
• Each carbon in the ring has two substituents: one is in an axial
position and the other in an equatorial position
92
this, the better!
Look at your chair confirmation. How many equatorial positions
are there and how many axial positions are there?
Hello
this, the better!
Answer:
Hello
6 axial (red): 3 on top, 3 on bottom

6 equatorial (blue): 3 on top, 3 on bottom
this, the better!
Answers
• Adding the axial substituents is easy, as they point straight up and
down, alternating around the ring.
Hello
• The equatorial groups are drawn off of the ring, and they run
parallel to the lines in the chair
Each carbon ALWAYS has: one equatorial position, one axial position, one bond
pointed up, and one bond pointed down.
Monosubstituted Cyclohexane
• When cyclohexane has one substituent, there are two possible
chair conformations,
ring flip
Hello
• Ring flipping occurs by rotation of all the C-‐C bonds in the ring.
Axial substituents become equatorial and vice versa.
Make a model of these at home. Prove it to yourself! 96
• Consider methylcyclohexane. The chair conformation where the

methyl group is equatorial is the more stable chair
Hello
• At room temperature, methylcyclohexane will be in the more

stable chair 95% of the time.
• In the axial position, the methyl group causes steric interactions

that destabilize the conformation.
97
Draw both chair conformations for each of the following
compounds
OH NH2
Br
Hello
a. b. c.
Cl Me
d. e. f.
Answer: Since each ring is monosubstituted, it doesn’t matter
what carbon you put the substituent on. I’ll demonstrate this by
putting my substituent on a different carbon each time.
Br OH NH2
OH H 2N
Br
Hello
a. b. c.
Cl
Me t-Bu
Cl Me t-Bu
d. e. f.
I can also draw all the same structures, but with every substituent
pointing down instead of every substituent pointing up.
• The steric strain from a substituent being in the axial position is
the result of 1,3-‐diaxial interactions
Hello
• The 1,3-‐diaxial interactions are actually gauche interactions,

which are not present when the methyl group is equatorial
Make sure this makes sense

when you are making models
100
Hello
Make some of these models. See for your self!

101
Disubstituted Cyclohexane
• With multiple substituents, solid or dashed wedges are used to show
positioning of the groups on the ring
Hello
• Realize the Cl group is UP in both possible chair conformations, and
the methyl group is DOWN
• Cl is ALWAYS up!
• Me is ALWYAS down!
• It doesn't matter where on the ring you draw them as long as the Me
is to the right of the Cl. 102
• Draw both chair conformations for the following molecule
Hello
• Draw the first chair by labeling the substituted carbons in the
given structure, then translating to a chair:
On carbon 1 the ethyl group is

up, and on carbon 2 the methyl
group is down
103
• To draw the other possible chair, we have to make sure that the
ethyl group (pointed up) will be equatorial, and the methyl group
(pointed down) will be axial
Hello
• So the two conformations are:
Which chair is more stable?

What is your reasoning?
Most Stable:
Et is larger than Me so it
would rather be equatorial 104
Menthol is a waxy crystalline substance obtained from
peppermint or other mint oils.
Draw both possible chair configurations and determine which
conformation is the most stable.
Hello
Answer: The most stable conformation is when all
the substituents are equatorial in order to avoid
any steric 1,3-‐diaxial interactions.
Me
HO Hello Me
OH
Least Stable Most Stable

For each compound below, draw both possible chair

configurations and determine which conformation is the most
stable.
Cl
Hello
Cl
a. b. c.
d. e.
Answers: The most stable conformation is when all the groups are
equatorial. If that is not possible, the larger group prefers
equatorial in order to minimize the steric 1,3-‐diaxial interactions.
The smaller substituent will be forced to the axial position.
Cl
Me
Cl Cl
Hello
Most stable, Most stable, b.
Me Cl
a.
all equatorial. largest group is 7.6 kcal for axial methyl c. Most stable
equatorial
2.0 kcal x 2 for two axial Cl’s
7.6 kcal > 2.0 kcals (Cl’s are axial)
Most stable Most stable,

22 kcal for an axial t-‐Bu
d. t-‐Bu grous are a great Clearly, these
e.
don't look like all equatorial.
7.6 kcal per axial methyl way to force a ring into they can physically
a specific chair
7.6 x 2 < 22 conformation exist this way.
One of the compounds below predominantly exists in a chair
conformation while the other exists primarily in a twist boat.
Explain using full sentences! (FYI, I love putting essay questions
like this on the test)
Hello
t-Bu t-Bu t-Bu t-Bu
a. b.
Answer: The t-‐butyl group is really large and prefers the equatorial
position. The 1,3-‐diaxial interactions are so strong that if an
equatorial position is not available, the molecule will twist in such
a way to alleviate some of the strain.
Hello
t-Bu t-Bu t-Bu t-Bu
a. b.
H
H
stable chair conformation

cis-trans Stereoisomerism
• When naming a disubstituted cycloalkane, use the prefix cis when

there are two groups on the same side of the ring, and trans
when two substituents are on opposite sides of a ring
Hello
• These two compounds are stereoisomers. Since they are 6-‐

member rings, they are best represented as chair conformations
cis-trans Stereoisomerism
• Each compound exists as two equilibrating chairs, spending more

time in the more stable chair conformation
Hello
Both have the same energy,

always one axial and one
equatorial
This is the lowest energy
conformation for the trans
isomer. Both are equatorial
Polycyclic Systems
• Decalin is two 6-‐member rings fused together
Hello
• The decalin sub-‐structure is found

in many naturally occurring
compounds, such as steroids
Polycyclic Systems
• There are many important structures that result when more than
one ring is fused together (recall bicycloalkanes)
Hello
• Camphor and Camphene are fragrant natural products isolated

from evergreens
Polycyclic Systems
• The structure of diamond is a network of 6-‐membered rings,

fused together.
Hello

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Chapter 4: Alkanes and Cycloalkanes

• Hydrocarbons –composed of hydrogen and carbon

• Hydrocarbons are saturated or unsaturated

• Saturated hydrocarbons: Contain no 𝛑 bonds, called alkanes.

• Unsaturated hydrocarbons: Contain a double bond, alkenes,

propane 1-propene 1-propyne

• Hydrocarbons are saturated or unsaturated

• Saturated hydrocarbons: Contain no 𝛑 bonds, called alkanes.

• Unsaturated hydrocarbons: Contain a double bond, alkenes,

• Many organic compounds have “common” names

• A systematic method to naming was developed for simplicity.

• The IUPAC system (pronounced “I-­‐YOU-­‐PACK”)

– Parent name (longest carbon chain)

Finding the Parent Chain

Finding the Parent Chain

Finding the Parent Chain

erm “cyclo” is used toBranches

Memorize 1 -­‐ 12

Finding the Parent Chain

Identify the parent in the following compound

Both parent chains are 10 carbons long so we cant choose a parent

nonane octane cyclopentane

Answer: b and c have the same parent chain; both octane.

2. Identify and name the substituents

Memorize these (1-­‐4 are the most common)

2. Identify and name the substituents

Substituents end in yl instead of ane.

Memorize these (1-­‐4 are the most common)

1. Name the parent cHello

methyl Parent = undecane

1. Identify and name the substituents

1. Identify and name the substituents

1. Identify and name the substituents

1. Identify and name the substituents

Memorize these (t-­‐Bu is very very common)

1. Identify and name the substituents

pentyl isopentyl (or isoamyl) neopentyl

Parent = heptane Parent = nonane

Parent = nonane Parent = undecane

• Carbons in the parent chain have to be numbered.

• Guidelines to follow when numbering the parent chain

• Guidelines to follow when numbering the parent chain

2. When multiple substituents are present, number the parent

• Guidelines to follow when numbering the parent chain

• Guidelines to follow when numbering the parent chain

• Guidelines to follow when numbering the parent chain

– The same rules apply for cycloalkanes

To assemble the complete name:

note: “di” or “tri” is ignored when alphabetizing the

1. Identify the parent chain

2. Identify and name the substituents

4. List the numbered substituents before the parent name in

4-­‐ethyl-­‐2,3-­‐dimethyloctane 3,4,6-­‐trimethyloctane sec-­‐butylcyclohexane

4-­‐tert-­‐butylheptane 1,3-­‐diisopropylcyclopentane 3-­‐ethyl-­‐2,5-­‐dimethylhepane

• Bicyclic compound contains two fused rings.

• There are three “paths” connecting the Bridgehead

Molecular Formula: C6H14 C6H14

Condensed Structure: CH3CH2CH2CH2CH3 CH(CH3)2CH2CH2CH3

IUPAC Name: hexane 2-methylpentane

• As the number of carbon

• Be able to recognize different structures as either being isomers,

same compound consKtuKonal isomers

+ 12.5 O2 8CO2 + 9H2O

• The IUPAC system (pronounced “I-‐YOU-‐PACK”)

Memorize 1 -‐ 12

Memorize these (1-‐4 are the most common)

Memorize these (1-‐4 are the most common)

Memorize these (t-‐Bu is very very common)

4-‐ethyl-‐2,3-‐dimethyloctane 3,4,6-‐trimethyloctane sec-‐butylcyclohexane

4-‐tert-‐butylheptane 1,3-‐diisopropylcyclopentane 3-‐ethyl-‐2,5-‐dimethylhepane

• Diesel fuel is a mixture of straight, branched hydrocarbons (12-‐20

• Single bonds rotate, resulting in multiple 3-‐D shapes, called

• If each H-‐-‐-‐-‐-‐H eclipsing interaction costs 4 kJ/mol of stability, that

• Each CH3-‐-‐-‐-‐-‐CH3 eclipsing interaction accounts for 11 kJ/mol of

• The combustion data for cycloalkanes shows that a 6-‐member

• The 1,3-‐diaxial interactions are actually gauche interactions,

• These two compounds are stereoisomers. Since they are 6-‐

• Decalin is two 6-‐member rings fused together

• The decalin sub-‐structure is found

• The structure of diamond is a network of 6-‐membered rings,