About The Authors

Chapter 4
These Powerpoint Lecture Slides were created and prepared by Professor
William Tam and his wife Dr. Phillis Chang.

Nomenclature & Professor William Tam received his B.Sc. at the University of Hong Kong in
1990 and his Ph.D. at the University of Toronto (Canada) in 1995. He was an
NSERC postdoctoral fellow at the Imperial College (UK) and at Harvard
Conformations of University (USA). He joined the Department of Chemistry at the University of
Guelph (Ontario, Canada) in 1998 and is currently a Full Professor and
Associate Chair in the department. Professor Tam has received several awards
Alkanes & Cycloalkanes in research and teaching, and according to Essential Science Indicators, he is
currently ranked as the Top 1% most cited Chemists worldwide. He has
published four books and over 80 scientific papers in top international journals
such as J. Am. Chem. Soc., Angew. Chem., Org. Lett., and J. Org. Chem.

Dr. Phillis Chang received her B.Sc. at New York University (USA) in 1994, her
Created by M.Sc. and Ph.D. in 1997 and 2001 at the University of Guelph (Canada). She
lives in Guelph with her husband, William, and their son, Matthew.
Professor William Tam & Dr. Phillis Chang
Ch. 4 - 1 Ch. 4 - 2

1. Introduction to Alkanes &
Alkanes: CnH2n+2

Cycloalkanes e.g.
5 3 1

6 4 2

Alkanes and cycloalkanes are
hexane (C6H14)
hydrocarbons in which all the carbon-
carbon (C–C) bonds are single bonds

Cycloalkanes: CnH2n

Hydrocarbons that contain
C═C: Alkenes e.g.
Hydrocarbons that contain
cyclohexane (C6H12)
C≡C: Alkynes
Ch. 4 - 3 Ch. 4 - 4

1A. Sources of Alkanes: Petroleum
Petroleum refining

Petroleum is the primary source of ● Distillation is the first step in

alkanes. It is a complex mixture of refining petroleum. Its components
mostly alkanes and aromatic are separated based on different
hydrocarbons with small amounts of volatility
oxygen-, nitrogen-, and sulfur-
containing compounds ● More than 500 different compounds
are contained in petroleum
distillates boiling below 200oC

Ch. 4 - 5 Ch. 4 - 6

Petroleum refining (Cont’d)
Gasoline
● The demand of gasoline is much
● The fractions taken contain a greater than that supplied by the
mixture of alkanes of similar boiling gasoline fraction of petroleum
points
● Converting hydrocarbons from other
fractions of petroleum into gasoline
● Mixture of alkanes can be used as by “catalytic cracking”
fuels, solvents, and lubricants
mixture of alkanes catalysts highly branched
o
(C12 and higher) ~ 500 C hydrocarbons
(C5 - C10)
Ch. 4 - 7 Ch. 4 - 8

Gasoline (Cont’d)
Gasoline (Cont’d)

CH3 CH3
CH3 C CH2 C CH3
CH3 H isooctane heptane
2,2,4-Trimethylpentane (isooctane)
(C12H18) "octane
rating" 100 0
● Isooctane burns very smoothly
(without knocking) in internal
● e.g. a gasoline of a mixture:
combustion engines and is used as
87% isooctane and 13% heptane
one of the standards by which the
 Rated as 87-octane gasoline
octane rating of gasoline is
established Ch. 4 - 9 Ch. 4 - 10

Typical Fractions Obtained by Typical Fractions Obtained by

Distillation of Petroleum Distillation of Petroleum
Boiling Range of # of Carbon Use (Cont’d)
Fraction (oC) Atoms per Boiling Range of # of Carbon Use
Molecule Fraction (oC) Atoms per
Below 20 C1 – C4 Natural gas, bottled Molecule
gas, petrochemicals 250 – 400 C12 and higher Gas oil, fuel oil, and
20 – 60 C5 – C6 Petroleum ether, diesel oil
solvents Nonvolatile liquids C20 and higher Refined mineral oil,
60 – 100 C6 – C7 Ligroin, solvents lubricating oil, and
grease
40 – 200 C5 – C10 Gasoline (straight-
run gasoline) Nonvolatile solids C20 and higher Paraffin wax,
asphalt, and tar
175 – 325 C12 – C18 Kerosene and jet
fuel
Ch. 4 - 11 Ch. 4 - 12
2. Shapes of Alkanes
“Straight-chain” (unbranched) alkanes

All carbon atoms in alkanes and

cycloalkanes are sp3 hybridized, and Butane Pentane
they all have a tetrahedral geometry
CH3CH2CH2CH3 CH3CH2CH2CH2CH3

Even “straight-chain” alkanes are not

straight. They have a zigzag geometry

Ch. 4 - 13 Ch. 4 - 14

Branched-chain alkanes
Butane and isobutane have the same

Isobutane Neopentane molecular formula (C4H10) but different
CH3 bond connectivities. Such compounds
CH3 CH CH3 CH3 C CH3 are called constitutional isomers
CH3 CH3

Butane Isobutane

Ch. 4 - 15 Ch. 4 - 16

C4 and higher alkanes exist as
Constitutional isomers usually have

constitutional isomers. The number of different physical properties
constitutional isomers increases rapidly Hexane Isomers (C6H14)
with the carbon number Formula M.P. B.P. Density Refractive
(oC) (oC) (g/mL) Index
Molecular # of Possible Molecular # of Possible
-95 68.7 0.6594 1.3748
Formula Const. Isomers Formula Const. Isomers
C4H10 2 C9H20 35 -153.7 60.3 0.6532 1.3714
C5H12 3 C10H22 75
-118 63.3 0.6643 1.3765
C6H14 5 C20H42 366,319
-128.8 58 0.6616 1.3750
C7H16 9 C40H82 62,481,801,147,341
-98 49.7 0.6492 1.3688
C8H18 18
Ch. 4 - 17 Ch. 4 - 18
3. IUPAC Nomenclature of Alkanes,
Although the IUPAC naming system is
Alkyl Halides, & Alcohols now widely accepted among chemists,

One of the most commonly used common names (trivial names) of
nomenclature systems that we use some compounds are still widely used
today is based on the system and rules by chemists and in commerce. Thus,
developed by the International Union learning some of the common names
of Pure and Applied Chemistry (IUPAC) of frequently used chemicals and
compounds is still important

Fundamental Principle: Each different
compound shall have a unique name

Ch. 4 - 19 Ch. 4 - 20

The ending for all the names of
Unbranched alkanes

alkanes is –ane
Name Structure Name Structure

The names of most alkanes stem from Methane CH4 Hexane CH3(CH2)4CH3
Greek and Latin Ethane CH3CH3 Heptane CH3(CH2)5CH3

one two three four five Propane CH3CH2CH3 Octane CH3(CH2)6CH3

Butane CH3CH2CH2CH3 Nonane CH3(CH2)7CH3
meth- eth- prop- but- pent- Pentane CH3(CH2)3CH3 Decane CH3(CH2)8CH3

Ch. 4 - 21 Ch. 4 - 22

3A. Nomenclature of Unbranched
Alkyl group (Cont’d)

Alkyl Groups ● For an unbranched alkane, the
hydrogen atom that is removed is a

Alkyl group terminal hydrogen atom
● Removal of one hydrogen atom CH3 H CH3CH2 H CH3CH2CH2 H
from an alkane Methane Ethane Propane

CH3 CH3CH2 CH3CH2CH2

Methyl Ethyl Propyl
(Me) (Et) (Pr)
Ch. 4 - 23 Ch. 4 - 24
3B. Nomenclature of Branched-
Branched-Chain
Rule (Cont’d)
Alkanes 2. Use the lowest number of the

Rule substituent
1. Use the longest continuous carbon 3. Use the number obtained by
chain as parent name Rule 2 to designate the location of
7 6 5 4 3 6 5 4 3 2 1 the substituent
CH3CH2CH2CH2CHCH3 CH3CH2CH2CH2CHCH3
7 6 5 4 3 1 2 3 4 5
2CH2 CH2 CH3CH2CH2CH2CHCH3 CH3CH2CH2CH2CHCH3
NOT
1 CH3 CH3 2CH2 6 CH2
NOT
(3-Methylheptane) (2-Ethylhexane) 1 CH3 7 CH3
(3-Methylheptane) (5-Methylheptane)
Ch. 4 - 25 Ch. 4 - 26

Rule (Cont’d)
Rule (Cont’d)

4. For two or more substituents, use
the lowest possible individual
2 4 6 8
numbers of the parent chain 1 3 5 7
The substitutents should be listed (6-Ethyl-2-methyloctane)
alphabetically. In deciding
alphabetical order, disregard NOT NOT
multiplying prefix, such as “di”,
“tri” etc. 7 5 3 1 2 4 6 8
8 6 4 2 1 3 5 7
(3-Ethyl-7-methyloctane) (2-Methyl-6-ethyloctane)
Ch. 4 - 27 Ch. 4 - 28

Rule (Cont’d)
Rule (Cont’d)

5. When two substituents are present 6. For identical substituents, use
on the same carbon, use that prefixes di-, tri-, tetra- and so on
number twice 5 3 1
6 4 2 7 5 3 1
6 4 2

1
2
3
4
5
6
7
8 (2,4-Dimethylhexane) (2,4,5-Trimethylheptane)
(4-Ethyl-4-methyloctane)
NOT NOT
2 4 6
1 3 5 1 3 5 7
2 4 6

(3,5-Dimethylhexane) (3,4,6-Trimethylheptane)
Ch. 4 - 29 Ch. 4 - 30

Rule (Cont’d)
Rule (Cont’d)
7. When two chains of equal length 8. When branching first occurs at an
compete for selection as parent equal distance from either end of
chain, choose the chain with the the longest chain, choose the
greater number of substituents name that gives the lower number
at the first point of difference
7 1 1
6 4 2 4 2
5 3 3
6 1
NOT
5 5 3 1 2 4 6
NOT 6 4 2 3 5

7
(2,3,5-Trimethyl- (only three substituents) (2,3,5-Trimethylhexane) (2,4,5-Trimethylhexane)
4-propylheptane)
Ch. 4 - 31 Ch. 4 - 32

Example 1
Example 1 (Cont’d)

● Use the lowest numbering for
substituents
4 6 4 2
5 7 3 1
instead of
● Find the longest chain as parent 3 1 5
6
7
2

4 2 4 6
3 1 5 7
or ● Substituents: two methyl groups
5
6
7 3
2
1  dimethyl 4 6
5 7

3 1
2
Ch. 4 - 33 Ch. 4 - 34

Example 1 (Cont’d)
Example 2

● Complete name
4 6
5 7

3 1
2

(3,4-Dimethylheptane)

Ch. 4 - 35 Ch. 4 - 36

Example 2 (Cont’d)
Example 2 (Cont’d)
● Find the longest chain as parent ● Find the longest chain as parent

9-carbon chain
(correct!)
6-carbon chain 8-carbon chain 8-carbon chain
⇒ Nonane as parent
Ch. 4 - 37 Ch. 4 - 38

Example 2 (Cont’d)
Example 2 (Cont’d)

● Use the lowest numbering for ● Substituents
substituents  3,7-dimethyl
8 2  4-ethyl
7 3
9 1 8
7
6 4
5 instead of 5 9
2 8 6
3 7 6 5
4
1 9 2
3
4
1
(3,4,7) (3,6,7)

Ch. 4 - 39 Ch. 4 - 40

Example 2 (Cont’d) 3C. Nomenclature of Branched Alkyl

● Substituents in alphabetical order Groups
 Ethyl before dimethyl
For alkanes with more than two carbon
(recall Rule 4 – disregard “di”) atoms, more than one derived alkyl
● Complete name group is possible
7
8
Three-carbon groups
9
6
5
2
3
4 Propyl Isopropyl
1
(or 1-methylethyl)
(4-Ethyl-3,7-dimethylnonane)
Ch. 4 - 41 Ch. 4 - 42

Four-carbon groups
A neopentyl group

Butyl Isobutyl
neopentyl
(2,2,-dimethylpropyl)

sec-butyl tert-butyl
(1-methylpropyl) (or 1,1-dimethylethyl)
Ch. 4 - 43 Ch. 4 - 44

Example 1
Example 1 (Cont’d)

● Find the longest chain as parent
(a) (b)

6-carbon 7-carbon
chain chain

(c) (d)

8-carbon 9-carbon
chain chain
Ch. 4 - 45 Ch. 4 - 46

Example 1 (Cont’d)
Example 1 (Cont’d)

● Find the longest chain as parent ● Use the lowest numbering for
(d) substituents

⇒ Nonane as parent 1 2 3 4 5 6 7 8 9
or 9 8 7 6 5 4 3 2 1

5,6 4,5
1 3 4 5 6 7 8 9 9 7 6 5 4 3 2 1 (lower numbering)
2 or 8

⇒ Use 4,5
Ch. 4 - 47 Ch. 4 - 48

Example 1 (Cont’d)
Example 1 (Cont’d)
● Substituents ● Alphabetical order of substituents
 Isopropyl  tert-butyl before isopropyl
 tert-butyl
● Complete name
9 8 7 6 5 4 3 2 1
9 8 7 6 5 4 3 2 1

⇒ 4-isopropyl and 5-tert-butyl 5-tert-Butyl-4-isopropylnonane

Ch. 4 - 49 Ch. 4 - 50

Example 2
Example 2 (Cont’d)

● Find the longest chain as parent
(a) (b)

8-carbon 9-carbon
chain chain

(c)
⇒ Octane as parent

10-carbon
chain
Ch. 4 - 51 Ch. 4 - 52

Example 2 (Cont’d)
Example 2 (Cont’d)

● Use the lowest numbering for
substituents
1 2 3 4 5 6 7 8 9
10
5,6
1 2 3 4 5 6 7 8 9
10
or
or 5,6
10 9 8 7 6 5 4 3 2
1
10 9 8 7 6 5 4 3 2
1
⇒ Determined using
the next Rules
Ch. 4 - 53 Ch. 4 - 54

Example 2 (Cont’d)
Example 2 (Cont’d)
● Substituents ● Since sec-butyl takes precedence
 sec-butyl over neopentyl
 Neopentyl  5-sec-butyl and 6-neopentyl

● Complete name

But is it 10 9 8 7 6 5 4 3 2
1
● 5-sec-butyl and 6-neopentyl or
● 5-neopentyl and 6-sec-butyl ?
Ch. 4 - 55 5-sec-Butyl-6-neopentyldecane Ch. 4 - 56

3D. Classification of Hydrogen Atoms 3E. Nomenclature of Alkyl Halides

Rules
1o hydrogen atoms ● Halogens are treated as
substituents (as prefix)
CH3 F: fluoro Br: bromo
Cl: chloro I: iodo
CH3 CH CH2 CH3
● Similar rules as alkyl substituents
3o hydrogen atoms 2o hydrogen atoms

Ch. 4 - 57 Ch. 4 - 58

Examples 3F. Nomenclature of Alcohols

4
3
2
1
IUPAC substitutive nomenclature:
Cl a name may have as many as four
Br features
2-Bromo-1-chlorobutane
● Locants, prefixes, parent compound,
Cl and suffixes
2 6
Cl 1 3 4 5

CH3 6 5 4 3 2 1 OH
1,4-Dichloro-3-methylhexane 4-Methyl-1-hexanol

Ch. 4 - 59 Ch. 4 - 60

Rules
Examples
● Select the longest continuous carbon OH
chain to which the hydroxyl is directly OH
2 1
attached. Change the name of the 3 1 4 3 2 OH
alkane corresponding to this chain by 2-Propanol OH
dropping the final –e and adding the (isopropyl alcohol) 1,2,3-Butanetriol
suffix –ol
● Number the longest continuous carbon 5 1
4 3 2
chain so as to give the carbon atom OH
bearing the hydroxyl group the lower
4-Methyl-1-pentanol
number. Indicate the position of the
(or 4-Methylpentan-1-ol)
hydroxyl group by using this number as
(NOT 2-Methyl-5-pentanol)
a locant Ch. 4 - 61 Ch. 4 - 62

Example 4
Example 4 (Cont’d)

● Find the longest chain as parent
8
7
6
3 1 or 1 5 7
4 2 2 4 6
5 3
OH
OH OH
Longest chain but 7-carbon chain
does not contain containing the
the OH group OH group

⇒ Heptane as parent
Ch. 4 - 63 Ch. 4 - 64

Example 4 (Cont’d)
Example 4 (Cont’d)

● Use the lowest numbering for the ● Parent and suffix
carbon bearing the OH group  2-Heptanol
1 5 7
2 4 6
3
● Substituents
OH
1
2 4
5
6
7
or
7
6 4
3
2
1  Propyl
3 5

OH 2,3 OH 5,6
(lower numbering) ● Complete name
 3-Propyl-2-heptanol
⇒ Use 2,3
Ch. 4 - 65 Ch. 4 - 66
4. How to Name Cycloalkanes
Substituted cycloalkanes

4A. Monocyclic Compounds

Cycloalkanes with only one ring
● Attach the prefix cyclo- Isopropylcyclopropane Methylcyclopropane

H2C CH2 = H2C CH2 =

C H2C CH2
H2 C
Cyclopropane H2
Cyclopentane tert-Butylcyclopentane
Ch. 4 - 67 Ch. 4 - 68

Example 1
Example 2
Br
3 1-Ethyl-3-methyl-
4 2 5 4 3 4-Bromo-2-ethyl-1-methyl
cyclopentane 2
5 1
6 1 cyclohexane

NOT NOT NOT Br

3 4 5 5 1 2 6 1 2 1-Bromo-3-ethyl-4-methyl
1 3 3
2 4
5 4 cyclohexane
1-Ethyl-4-methyl- 3-Ethyl-1-methyl- (lowest numbers of substituents
cyclopentane cyclopentane are 1,2,4 not 1,3,4)
Ch. 4 - 69 Ch. 4 - 70

Example 3
Cycloalkylalkanes
● When a single ring system is
4
3 2 4-Ethyl-3-methyl attached to a single chain with a
1 cyclohexanol
5 6 greater number of carbon atoms
OH

NOT 1-Cyclobutylpentane

1
2 3 1-Ethyl-2-methyl
4 cyclohexan-4-ol
6 5 ● When more than one ring system
OH
is attached to a single chain
(the carbon bearing the OH should have the lowest
numbering, even though 1,2,4 is lower than 1,3,4) 1,3-Dicyclohexylpropane
Ch. 4 - 71 Ch. 4 - 72
4B. Bicyclic Compounds
Example (Cont’d)

Bicycloalkanes
● Alkanes containing two fused or
bridged rings

Between the two bridgeheads
● Two-carbon bridge on the left
● Two-carbon bridge on the right

Total # of carbons = 7 ● One-carbon bridge in the middle
● Bicycloheptane

Complete name

Bridgehead ● Bicyclo[2.2.1]heptane
Ch. 4 - 73 Ch. 4 - 74

Other examples 5. Nomenclature of Alkenes &

2
9 1
3
Cycloalkenes
8
7
6 4
Rule
5
1. Select the longest chain that
7-Methylbicyclo[4.3.0]nonane contains C=C as the parent name
8 and change the name ending of
7 the alkane of identical length from
4
5 3 –ane to
1
–ene
6 2

1-Isopropylbicyclo[2.2.2]octane
Ch. 4 - 75 Ch. 4 - 76

Rule ● Examples
2. Number the chain so as to include
1 2 3 4
both carbon atoms of C=C, and CH2 CHCH2CH3
begin numbering at the end of the 1-Butene
chain nearer C=C. Assign the (not 3-Butene)
location of C=C by using the
number of the first atom of C=C
1 2 3 4 5 6
as the prefix. The locant for the CH3CH CHCH2CH2CH3
alkene suffix may precede the 2-Hexene
parent name or be placed (not 4-Hexene)
immediately before the suffix
Ch. 4 - 77 Ch. 4 - 78

Rule ● Examples (Cont’d)
3. Indicate the locations of the
4 6
substituent groups by the numbers 3 5

of the carbon atoms to which they 2

1
are attached 2,5-Dimethyl-2-hexene
● Examples
4
3 3 1
NOT 4 2
2
1 5
6
2-Methyl-2-butene
2,5-Dimethyl-4-hexene
(not 3-Methyl-2-butene)
Ch. 4 - 79 Ch. 4 - 80

Rule ● Example
4. Number substituted cycloalkenes 6
1
2
in the way that gives the carbon
atoms of C=C the 1 and 2 5
4
3

positions and that also gives the 3,5-Dimethylcyclohexene

substituent groups the lower
numbers at the first point of
2
difference NOT 3 1

4 6
5
4,6-Dimethylcyclohexene
Ch. 4 - 81 Ch. 4 - 82

Rule ● Examples (Cont’d)

5. Name compounds containing a
C=C and an alcohol group as OH
alkenols (or cycloalkenols) and
4 2
give the alcohol carbon the lower 5 3 1

number 4-Methyl-3-penten-2-ol
(or 4-Methylpent-3-en-2-ol)
● Examples OH
6 1
2
5
3
4
2-Methyl-2-cyclohexen-1-ol
(or 2-Methylcyclohex-2-en-1-ol)
Ch. 4 - 83 Ch. 4 - 84

Rule
Rule
6. Vinyl group & allyl group 7. Cis vs. Trans
Vinyl group Allyl group ● Cis: two identical or substantial
groups on the same side of C=C
ethenyl prop-2-en-1-yl ● Trans: two identical or
OH substantial groups on the
6 1 2
opposite side of C=C
5
3 Cl
Ethenylcyclopropane 4
(or Vinylcyclopropane) 3-(Prop-2-en-1-yl) Cl Cl Cl
cyclohexan-1-ol cis-1,2-Dichloroethene trans-1,2-Dichloroethene
(or 3-Allylcyclohexanol)
Ch. 4 - 85 Ch. 4 - 86

Example
Example (Cont’d)

6 (a) (b)
5 7
6
4 2 4 2
3 1 5 3 1

(c) (d)

6 2
4 2 4 6
7 5 3 1 1 3 5 7

Ch. 4 - 87 Ch. 4 - 88

Example (Cont’d) 6. Nomenclature of Alkynes

● Complete name

Alkynes are named in much the same
way as alkenes, but ending name with
2
–yne instead of –ene
4 6
1 3 5 7

Examples
4-tert-Butyl-2-methyl-1-heptene
3 2 2 3
6 4 1
Br
1
7 5 4

2-Heptyne 4-Bromo-1-butyne
Ch. 4 - 89 Ch. 4 - 90

Examples (Cont’d)
OH group has priority over C≡C
4 3 1 2
2 3
OH NOT OH
3 4
I Br 1 4
2
5 6 7 8 9
3-Butyn-1-ol
1 10

9-Bromo-7-iodo-6-isopropyl-8-methyl-3-decyne OH 5 6 7 OH 4 3 2
2 4 7 5
1 3 8 8 6 1
2-Methyl-5-octyn-2-ol NOT

Ch. 4 - 91 Ch. 4 - 92

7. Physical Properties of C6H14 Isomer Boiling Point (oC)

Alkanes & Cycloalkanes
68.7

Boiling points & melting points
63.3

60.3

58

49.7
Ch. 4 - 93 Ch. 4 - 94

Physical Constants of Cycloalkanes 8. Sigma Bonds & Bond Rotation

# of C Refractive
Two groups bonded by a single bond
Atoms Name bp (oC) mp (oC) Density Index
can undergo rotation about that bond
3 Cyclopropane -33 -126.6 - -
with respect to each other
4 Cyclobutane 13 -90 - 1.4260 ● Conformations – temporary molecular
shapes result from a rotation about a single
5 Cyclopentane 49 -94 0.751 1.4064 bond
● Conformer – each possible structure of
6 Cyclohexane 81 6.5 0.779 1.4266 conformation
● Conformational analysis – analysis of
7 Cycloheptane 118.5 -12 0.811 1.4449
energy changes occur as a molecule
8 Cyclooctane 149 13.5 0.834 -
undergoes rotations about single bonds
Ch. 4 - 95 Ch. 4 - 96
 8A. Newman Projections 8B. How to Do a Conformational Analysis

Me
H H Sawhorse formula

Cl OH
Et
Look from this
direction Look from this
H Me H H direction
combine Me H φ1 = 60o
Cl Et OH Cl Et a
H
front carbon back carbon OH
H H
b staggered
Newman Projection φ2 = 180o confirmation
H H of ethane
Hc
Ch. 4 - 97 Ch. 4 - 98

60o 0o CH3
CH3 CH3 CH3
CH3
180o Look from this
direction
CH3
φ = 0o
anti gauche eclipsed
HH
eclipsed
confirmation
H H of ethane
H H
Ch. 4 - 99 Ch. 4 - 100

9. Conformational Analysis of
Butane

H Me
Me H H H

H Me H H
H Me
Sawhorse formula New Projection
formula

Ch. 4 - 101 Ch. 4 - 102

 CH3
CH3 H CH3
H H


CH3 H

H H H H H H
CH3 CH3 H H
anti conformer eclipsed conformer gauche conformer
(I) (II) (III)
(lowest energy)


= CH3 on front carbon

rotates 60o clockwise

CH3 CH3
H CH3 H3C

H CH3

H H H H H H
H CH3 H H H
eclipsed conformer gauche conformer eclipsed conformer
(VI) (V) (IV)
(highest energy)
Ch. 4 - 103 Ch. 4 - 104

10. The Relative Stabilities of 10

10A.
A. Cyclopropane
Cycloalkanes: Ring Strain H H
sp3 hybridized carbon

Cycloalkanes do not have the same θ
H H (normal tetrahedral
relative stability due to ring strain bond angle is 109.5o)

Ring strain comprises:
H H
● Angle strain – result of deviation from
ideal bond angles caused by inherent
Internal bond angle (θ) ~60o (~49.5o
structural constraints
deviated from the ideal tetrahedral
● Torsional strain – result of dispersion
forces that cannot be relieved due to
angle)
restricted conformational mobility
Ch. 4 - 105 Ch. 4 - 106

10
10B.
B. Cyclobutane
H H
θ
H
H H
H
H
H

Internal bond angle (θ) ~88o (~21o
deviated from the normal 109.5o
tetrahedral angle)

Ch. 4 - 107 Ch. 4 - 108


Cyclobutane ring is not planar but is 10
10C.
C. Cyclopentane
slightly folded. H H
H
HH HH

If cyclobutane ring were planar, the
angle strain would be somewhat less H
(the internal angles would be 90o H H
instead of 88o), but torsional strain
If cyclopentane were planar, θ ~108o, very close
would be considerably larger because to the normal tetrahedral angle of 109.5o
all eight C–H bonds would be eclipsed
However, planarity would introduce considerable
torsional strain (i.e. 10 C–H bonds eclipsed)

Therefore cyclopentane has a slightly bent
conformation
Ch. 4 - 109 Ch. 4 - 110

11. Conformations of Cyclohexane:
The boat conformer of cyclohexane is

The Chair & the Boat less stable (higher energy) than the
6 2 3
chair form due to
4
5
3D ● Eclipsed conformation
6 5
1
2
3 1 4
● 1,4-flagpole interactions
(chair form) (boat form)
(more stable) (less stable) 1
H H 4

H H H H H H
H
4
H H H
5 3
5
6 2
3 6 4 2 H H
H H HH HH
H
1
H 1 (eclipsed)
Ch. 4 - 111 Ch. 4 - 112

Energy diagram

(twist boat)

The twist boat conformation has a

lower energy than the pure boat
conformation, but is not as stable as
the chair conformation

Ch. 4 - 113 Ch. 4 - 114

12. Substituted Cyclohexanes: Axial
Substituted cyclohexane
& Equatorial Hydrogen Atoms ● Two different chair forms
H

Equatorial hydrogen atoms in chair
form H G
H H
H H H
H G

Axial hydrogen atoms in chair form H

H H
H G H
(equatorial G) (axial G) G
H (more stable) (less stable)
H H Ch. 4 - 115 Ch. 4 - 116

The chair conformation with axial G is

G
less stable due to 1,3-diaxial
interaction 1,3-diaxial interaction (equatorial) (axial) G

H G
3 H At 25oC
1 H G % of Equatorial % of Axial

The larger the G group, the more F 60 40
severe the 1,3-diaxial interaction and CH3 95 5
shifting the equilibrium from the axial- iPr 97 3
G chair form to the equatorial-G chair tBu > 99.99 < 0.01
form Ch. 4 - 117 Ch. 4 - 118

13. Disubstituted Cycloalkanes 13

13A.
A.Cis
Cis--Trans Isomerism & Conformation
Structures of Cyclohexanes
Cis-Trans Isomerism
H H H CH3
Trans-1,4-Disubstituted Cyclohexanes

CH3 CH3 CH3 H CH3 H

cis-1,2-Dimethyl trans-1,2-Dimethyl ring H3C
H
cyclopropane cyclopropane H CH3
flip
CH3 H
Cl Cl Cl H
trans-Diaxial trans-Diequatorial
H H H Cl
cis-1,2-Dichloro trans-1,2-Dichloro
cyclobutane cyclobutane
Ch. 4 - 119 Ch. 4 - 120
 Upper bond
H
Cis-1,4-Disubstituted Cyclohexanes
CH3 trans-Dimethyl
H3C cyclohexane
CH3 chair-chair CH3
H ring
H H
Lower bond H3C flip CH3
H H

Upper-lower bonds means the groups
Equatorial-axial Axial-equatorial
are trans

Ch. 4 - 121 Ch. 4 - 122

Cis-1-tert-Butyl-4-methylcyclohexane
Trans-1,3-Disubstituted Cyclohexanes

H3C (ax)
CH3 CH3
CH3 H3C
CH3 ring (eq) ring H
H
H3C CH3 H3C H flip
flip CH3
H3C H CH3 (eq)
(more stable (less stable (ax)
because large because large
group is group is trans-1,3-Dimethylcyclohexane
equatorial) axial)
Ch. 4 - 123 Ch. 4 - 124

Trans-1-tert-Butyl-3-methylcyclohexane
Cis-1,3-Disubstituted Cyclohexanes

H3C
CH3
H3C H
CH3 ring H ring
H3C CH3
flip CH3 H H
H3C flip
CH3 CH3
CH3 CH3
(more stable (less stable (more stable) (less stable)
because large because large
group is group is
equatorial) axial)
Ch. 4 - 125 Ch. 4 - 126

Trans-1,2-Disubstituted Cyclohexanes
Cis-1,2-Disubstituted Cyclohexane
(ax) (ax) (ax)
(eq) CH3 CH3
ring CH3
CH3 ring
CH3 flip (ax) CH3 flip CH3
(eq) (eq) (eq)
CH3
diequatorial diaxial (equatorial-axial) (axial-equatorial)
(much more stable) (much less stable)
cis-1,2-Dimethylcyclohexane
trans-1,2-Dimethylcyclohexane (equal energy and equally
populated conformations)
Ch. 4 - 127 Ch. 4 - 128

14. Bicyclic & Polycyclic Alkanes

Decalin
(Bicyclo[4.4.0]decane)

H H Adamantane Cubane Prismane

H H
cis-Decalin trans-Decalin
H H
H

C60 (Buckminsterfullerene)
H Ch. 4 - 129 Ch. 4 - 130

16. Synthesis of Alkanes and
Examples

Cycloalkanes Ni
+ H2
EtOH H H
16
16A.
A.Hydrogenation
Hydrogenation of Alkenes & Alkynes o
H2 25 C, 50 atm.
H H H
Pt, Pd or Ni Pd
C C + H2
solvent
heat and pressure EtOH H
o
25 C, 1 atm.
2H2 H H
H H Pd
Pt, Pd or Ni
C C
solvent EtOAc H H
heat and pressure H H o
+ 2 H2 65 C, 1 atm.
Ch. 4 - 131 Ch. 4 - 132
17. How to Gain Structural Information
from Molecular Formulas & Index
Index of hydrogen deficiency (Cont’d)
of Hydrogen Deficiency
● Saturated acyclic alkanes: CnH2n+2

Index of hydrogen deficiency (IHD)
● The difference in the number of pairs of
hydrogen atoms between the ● Each double bond on ring:
compound under study and an acyclic 2 hydrogens less
alkane having the same number of
carbons ● Each double bond on ring provides
one unit of hydrogen deficiency
● Also known as “degree of unsaturation”
or “double-bond equivalence” (DBE)
Ch. 4 - 133 Ch. 4 - 134

e.g. Hexane: C6H14
Examples

and C6H12
IHD = 2 IHD = 3
1-Hexene Cycloheane
C6H14
Index of hydrogen – C6H12
=
deficiency (IHD) H2
= one pair of H2 IHD = 2 IHD = 4
=1
Ch. 4 - 135 Ch. 4 - 136

16
16A.
A.Compounds
Compounds Containing Halogen,
Example 1: IHD of C4H6Cl2
Oxygen, or Nitrogen ● Count Cl as H
C4H10

For compounds containing  C4H6Cl2 ⇒ C4H8
– C4H8
● Halogen – count halogen atoms as ● A C4 acyclic alkane:
though they were hydrogen atoms C4H2(4)+2 = C4H10 H2
● Oxygen – ignore oxygen atoms
IHD of C4H6Cl2 = one pair of H2 = 1
and calculate IHD from the
remainder of the formula ● Possible structures
● Nitrogen – subtract one hydrogen Cl
for each nitrogen atom and ignore Cl or or
Cl Cl
nitrogen atoms ... etc. Cl Cl
Ch. 4 - 137 Ch. 4 - 138

Example 2: IHD of C5H8O
Example 3: IHD of C5H7N
● Ignore oxygen ● Subtract 1 H for each N
C5H12 C5H12
 C5H8O ⇒ C5H8  C5H7N ⇒ C5H6
– C5H8 – C5H6
● A C5 acyclic alkane: ● A C5 acyclic alkane:
C5H2(5)+2 = C5H12 H4 C5H2(5)+2 = C5H12 H6

IHD of C4H6Cl2 = two pair of H2 = 2 IHD of C4H6Cl2 = three pair of H2 = 3

● Possible structures ● Possible structures
O
or OH or or ... etc.
OH N C N
... etc. CH3
Ch. 4 - 139 Ch. 4 - 140

 END OF CHAPTER 4 

Ch. 4 - 141