Nomenclature &

Conformations of
Alkanes & Cycloalkanes

We will consider:
❖ How to name many simple organic molecules

❖ The flexible, three-dimensional nature of organic molecules

❖ An organic reaction that can convert alkenes and alkynes

to alkanes © 2014 by John Wiley & Sons, Inc. All rights reserved.
Introduction to Alkanes &
Cycloalkanes
❖ Alkanes and cycloalkanes are hydrocarbons in which
all the carbon-carbon (C–C) bonds are single bonds

❖ Alkanes: CnH2n+2 ❖ Cycloalkanes: CnH2n

5 3 1
e.g.
6 4 2
e.g.
hexane (C6H14) cyclohexane (C6H12)

❖ Hydrocarbons that contain Hydrocarbons that contain

C═C: Alkenes C≡C: Alkynes
Sources of Alkanes: Petroleum
Typical Fractions Obtained by
Distillation of Petroleum
Boiling Range of # of Carbon Atoms Use
Fraction (oC) per Molecule
Below 20 C1 – C4 Natural gas, bottled gas,
petrochemicals
20 – 60 C5 – C6 Petroleum ether, solvents
60 – 100 C6 – C7 Ligroin, solvents
40 – 200 C5 – C10 Gasoline (straight-run gasoline)
175 – 325 C12 – C18 Kerosene and jet fuel

250 – 400 C12 and higher Gas oil, fuel oil, and diesel oil

Nonvolatile liquids C20 and higher Refined mineral oil, lubricating oil,
and grease
Nonvolatile solids C20 and higher Paraffin wax, asphalt, and tar
❖ Gasoline (Cont’d)

isooctane heptane

"octane
rating" 100 0

● e.g. a gasoline of a mixture:

87% isooctane and 13% heptane
⧫ Rated as 87-octane gasoline

© 2014 by John Wiley & Sons, Inc. All rights reserved.

Shapes of Alkanes
❖ All carbon atoms are sp3 hybridized, and they all
have a tetrahedral geometry

❖ “Straight-chain” (unbranched) alkanes

Butane Pentane zigzag geometry

CH3CH2CH2CH3 CH3CH2CH2CH2CH3

❖ Branched-chain alkanes
Isobutane Neopentane
CH3
CH3 CH CH3 CH3 C CH3
CH3 CH3
❖ Butane and isobutane have the same molecular formula
(C4H10) but different bond connectivities. Such compounds
are called constitutional isomers

Butane Isobutane
❖ C4 and higher alkanes exist as constitutional isomers. The
number of constitutional isomers increases rapidly with the
carbon number

Molecular # of Possible Molecular # of Possible

Formula Const. Isomers Formula Const. Isomers
C4H10 2 C9H20 35
C5H12 3 C10H22 75
C6H14 5 C20H42 366,319
C7H16 9 C40H82 62,481,801,147,341
C8H18 18
❖ Constitutional isomers usually have
different physical properties
Hexane Isomers (C6H14)
Formula M.P. B.P. Density Refractive
(oC) (oC) (g/mL) Index
-95 68.7 0.6594 1.3748

-153.7 60.3 0.6532 1.3714

-118 63.3 0.6643 1.3765

-128.8 58 0.6616 1.3750

-98 49.7 0.6492 1.3688

© 2014 by John Wiley & Sons, Inc. All rights reserved.

How to Name Alkanes, Alkyl Halides,
and Alcohols: The IUPAC System

❖ International Union of Pure and

Applied Chemistry (IUPAC)

❖ Fundamental Principle: Each different

compound shall have a unique name
❖ The ending for all the names of alkanes is –ane

❖ The names of most alkanes stem from Greek and Latin

one two three four five

meth- eth- prop- but- pent-

❖ Unbranched alkanes
Name Structure Name Structure
Methane CH4 Hexane CH3(CH2)4CH3
Ethane CH3CH3 Heptane CH3(CH2)5CH3
Propane CH3CH2CH3 Octane CH3(CH2)6CH3
Butane CH3CH2CH2CH3 Nonane CH3(CH2)7CH3
Pentane CH3(CH2)3CH3 Decane CH3(CH2)8CH3
How to Name Unbranched Alkyl Groups
❖ Alkyl group: Removal of one hydrogen atom
from an alkane

CH3 H CH3CH2 H CH3CH2CH2 H

Methane Ethane Propane

CH3 CH3CH2 CH3CH2CH2

Methyl Ethyl Propyl
(Me) (Et) (Pr)
How to Name Branched-Chain Alkanes
❖ Rule
1. Use the longest continuous carbon chain
as parent name

7 6 5 4 3 6 5 4 3 2 1
CH3CH2CH2CH2CHCH3 CH3CH2CH2CH2CHCH3
2CH2 CH2
NOT
1 CH3 CH3
(3-Methylheptane) (2-Ethylhexane)
 2. Use the lowest number of the substituent

3. Use the number obtained by Rule 2 to

designate the location of the substituent

7 6 5 4 3 1 2 3 4 5
CH3CH2CH2CH2CHCH3 CH3CH2CH2CH2CHCH3
2CH2 6 CH2
NOT
1 CH3 7 CH3
(3-Methylheptane) (5-Methylheptane)
4. For two or more substituents, use the lowest
possible individual numbers of the parent chain.
The substituents should be listed alphabetically.

In deciding alphabetical order, disregard multiplying prefix,

such as “di”, “tri” etc.

2 4 6 8
1 3 5 7
(6-Ethyl-2-methyloctane)

NOT NOT

7 5 3 1 2 4 6 8
8 6 4 2 1 3 5 7
(3-Ethyl-7-methyloctane) (2-Methyl-6-ethyloctane)
5. When two substituents are present on the same carbon, use
that number twice
2 4 6 8
1 3 5 7
(4-Ethyl-4-methyloctane)

6. For identical substituents, use prefixes di-, tri-, tetra- and so on

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

(2,4-Dimethylhexane) (2,4,5-Trimethylheptane)

NOT NOT
2 4 6
1 3 5 1 3 5 7
2 4 6

(3,5-Dimethylhexane) (3,4,6-Trimethylheptane)
7. When two chains of equal length compete for
selection as parent chain, choose the chain with
the greater number of substituents

7 1 1
6 4 2 4 2
5 3 3

5
NOT 6
7
(2,3,5-Trimethyl- (only three substituents)
4-propylheptane)
 8. When branching first occurs at an equal
distance from either end of the longest
chain, choose the name that gives the lower
number at the first point of difference

6 1
NOT
5 3 1 2 4 6
4 2 3 5

(2,3,5-Trimethylhexane) (2,4,5-Trimethylhexane)

© 2014 by John Wiley & Sons, Inc. All rights reserved.

❖ Example 1

● Find the longest chain as parent

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

● Use the lowest numbering for substituents

4 6 4 2
5 7 3 1
instead of
3 1 5 7
2 6
❖ Example 1 (Cont’d)
● Substituents: two methyl groups
⧫ dimethyl 4 6
5 7

3 1
2

● Complete name
4 6
5 7

3 1
2

(3,4-Dimethylheptane)
❖ Example 2

● Find the longest chain as parent

6-carbon chain 8-carbon chain 8-carbon chain

❖ Example 2 (Cont’d)
● Find the longest chain as parent

⇒ Nonane as parent
9-carbon chain
(correct!)
● Use the lowest numbering for substituents
8 2
7 3
9 1
6 4
5 instead of 5
2 8
3 7 6
4
1 9

(3,4,7) (3,6,7)
 8
❖ Example 2 (Cont’d) 7
9
● Substituents 6
5
⧫ 3,7-dimethyl 2
⧫ 4-ethyl 3
4
1

● Substituents in alphabetical order

⧫ Ethyl before dimethyl 8
7
(recall Rule 4 – disregard “di”) 9
● Complete name 6
5
2
3
4
1

(4-Ethyl-3,7-dimethylnonane)
How to Name Branched Alkyl Groups
❖ Three-carbon groups

Propyl Isopropyl
(or 1-methylethyl)
❖ Four-carbon groups

Butyl Isobutyl

sec-butyl tert-butyl
(1-methylpropyl) (or 1,1-dimethylethyl)
How to Name Alkyl Halides
● Halogens are treated as substituents (as prefix)
F: fluoro Br: bromo
Cl: chloro I: iodo
● Similar rules as alkyl substituents
3 1
4 2
Cl
Br
2-Bromo-1-chlorobutane
Cl
2 6
Cl 1 3 4 5

CH3
1,4-Dichloro-3-methylhexane
How to Name Alcohols
● Select the longest continuous carbon chain to which
the hydroxyl is directly attached.

● Change the name of the alkane corresponding to

this chain by dropping the final –e and adding the
suffix –ol

● Number the longest continuous carbon chain so as

to give the carbon atom bearing the hydroxyl group
the lower number.

● Indicate the position of the hydroxyl group.

❖ Examples
OH
OH
2 1
3 1 4 3 2 OH
2-Propanol OH
(isopropyl alcohol) 1,2,3-Butanetriol
5 1
4 3 2
OH

4-Methyl-1-pentanol
(or 4-Methylpentan-1-ol)
(NOT 2-Methyl-5-pentanol)
❖ Example

OH
● Find the longest chain as parent
8
7
6
3 1 or 1 5 7
4 2 2 4 6
5 3

OH OH
Longest chain but 7-carbon chain
does not contain the containing the OH
OH group group
⇒ Heptane as parent
❖ Example (Cont’d)
● Use the lowest numbering for the carbon
bearing the OH group

2 6
(lowest number
of the carbon bearing
the OH group)
⇒ Use 2
❖ Example (Cont’d)
● Parent and suffix
⧫ 2-Heptanol
1 5 7
2 4 6
3
● Substituents
⧫ Propyl
OH

● Complete name
⧫ 3-Propyl-2-heptanol
How to Name Cycloalkanes
● Attach the prefix cyclo-
H2C CH2 = H2C CH2 =
C H2C CH2
H2 C
Cyclopropane H2
Cyclopentane
❖ Substituted cycloalkanes
❖ Example 1

4 3 2
1-Ethyl-3-methyl-
1
cyclopentane
5

NOT NOT
3 4 5 5 1 2
2 1 4 3

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

NOT Br
6 1 2 1-Bromo-3-ethyl-4-methyl
5 4
3 cyclohexane
(lowest numbers of substituents
are 1,2,4 not 1,3,4)
❖ Example 3

4
3 2 4-Ethyl-3-methyl
5 6
1 cyclohexanol
OH

NOT

1
2 3 1-Ethyl-2-methyl
6 5
4 cyclohexan-4-ol
OH
(the carbon bearing the OH should have the lowest
numbering, even though 1,2,4 is lower than 1,3,4)

© 2014 by John Wiley & Sons, Inc. All rights reserved.

How to Name Bicyclic Cycloalkanes
❖ Bicycloalkanes
● Alkanes containing two fused or
bridged rings

Bicyclo [2.2.1] heptane

❖ Total # of carbons = 7
● Bicycloheptane
❖ Bridgehead
© 2014 by John Wiley & Sons, Inc. All rights reserved.
 1 2
9 3
8 4
7 6
5
8-Methylbicyclo [4.3.0] nonane

1 2
7 8 3
6
5 4
8-Methylbicyclo [3.2.1] octane

© 2014 by John Wiley & Sons, Inc. All rights reserved.

Practice problem
Write structures for the following bicyclic
alkanes:

a) Bicyclo [1.1.0] butane

b) 7-Methylbicyclo [2.2.1] heptane

© 2014 by John Wiley & Sons, Inc. All rights reserved.

How to Name Alkenes & Cycloalkenes
1. Select the longest chain that contains C=C as the
parent name and change the name ending of the
alkane of identical length from –ane to –ene
2. Number the chain so as to include both carbon
atoms of C=C, and begin numbering at the end of
the chain nearer C=C. Assign the location of C=C
by using the number of the first atom of C=C as
the prefix.
1 2 3 4 1 2 3 4 5 6
CH2 CHCH2CH3 CH3CH CHCH2CH2CH3
1-Butene 2-Hexene
(not 3-Butene) (not 4-Hexene)
3. Indicate the locations of the substituent groups by
the numbers of the carbon atoms to which they
are attached
4
3
2
1
2-Methyl-2-butene
(not 3-Methyl-2-butene)

4 6 3 1
3 5 NOT 4 2
2 5
1 6
2,5-Dimethyl-2-hexene 2,5-Dimethyl-4-hexene
 4. Number substituted cycloalkenes in the way that
gives the carbon atoms of C=C the 1 and 2
positions and that also gives the substituent
groups the lower numbers at the first point of
difference

1 2
6 2 NOT 3 1

5 3 4 6
4 5
3,5-Dimethylcyclohexene 4,6-Dimethylcyclohexene
5. Name compounds containing a C=C and an alcohol group
as alkenols (or cycloalkenols) and give the alcohol carbon
the lower number OH
6 1
2
5
3
4
2-Methyl-2-cyclohexen-1-ol
(or 2-Methylcyclohex-2-en-1-ol)
6. Cis vs. Trans Cl

Cl Cl Cl
cis-1,2-Dichloroethene trans-1,2-Dichloroethene
Alkene Nomenclature-2
7. Vinyl group & allyl group
 Practice problem

O
H

O
H
C
l
(a) (b) (c) (d)

(e) cis-3-Octene (g) Vinylcyclopentane

(f) trans-1-Chlorobut-2-ene (h) 1,2 Dichlorocyclohexene

© 2014 by John Wiley & Sons, Inc. All rights reserved.

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

2-Heptyne 4-Bromo-1-butyne

3 4
I Br
2
5 6 7 8 9
1 10

9-Bromo-7-iodo-6-isopropyl-8-methyl-3-decyne
Sigma Bonds & Bond Rotation
❖ Two groups bonded by a single bond can
undergo rotation about that bond with
respect to each other

● Conformations – temporary molecular shapes that

result from a rotation about a single bond

● Conformer – each possible structure of

conformation

● Conformational analysis – analysis of energy

changes that occur as a molecule undergoes
rotations about single bonds
Newman Projections & How to Draw Them
5 4 3 2 1 1

3 2

4 5
1
Me
H H Sawhorse formula
2
3

Cl OH
Et 4-5
Look from this
direction
H Me H H
combine Me H
Cl Et OH Cl Et
front carbon back carbon OH
Newman Projection
How to Do a Conformational Analysis

f1 = 60o

f2 = 180o
f = 0o
Conformational Analysis of Butane
 60o 0o CH3
CH3 CH3 CH3
CH3
180o
CH3
anti gauche eclipsed
The Relative Stabilities of Cycloalkanes:
Ring Strain
❖ Cycloalkanes do not have the same
relative stability due to ring strain

❖ Ring strain comprises:

● Angle strain – result of deviation from ideal
bond angles caused by inherent structural
constraints
● Torsional strain – result of dispersion forces
that cannot be relieved due to restricted
conformational mobility
Cyclopropane
H H
sp3 hybridized carbon
q (normal tetrahedral bond
H H angle is 109.5o)

H H Angle strain
❖ Internal bond angle (q) ~60o
(~49.5o deviated from the ideal tetrahedral angle)

Eclipsed H’s

Torsional strain
Cyclobutane
H H
q
H
H H
H
H
H
❖ Internal bond angle (q) ~88o
(~21o deviated from the normal 109.5o tetrahedral angle)

❖ Cyclobutane ring is not planar but is

slightly folded.
Cyclopentane
H H
H
HH HH

H
H H
❖ If cyclopentane were planar, q ~108o, very close to
the normal tetrahedral angle of 109.5o
❖ However, planarity would introduce considerable
torsional strain (i.e. 10 C–H bonds eclipsed)

❖ Therefore cyclopentane has a slightly bent

conformation
Conformations of Cyclohexane:
The Chair & the Boat
6 4 2 3
3D 5

2 6 5
1 3 1 4
(chair form) (boat form)
(more stable) (less stable)

H H H H
H
4
H H H
6 2 5 3
5 3 6 4 2
H H HH
H
1
H 1 HH
eclipsed
❖ Energy diagram
Substituted Cyclohexanes: Axial
& Equatorial Hydrogen Groups
❖ The chair conformation of a cyclohexane ring has
two distinct orientations for the bonds that project
from the ring: axial and equatorial
H H
H H
H H
Axial: perpendicular
to the plane of the H H Equatorial:
H H
ring H H Extend from the
perimeter of the ring
upH Hup
Hup H
Orientation (up-
down) alternates H H
down H
from one carbon to
the next.
H H
Hdown H down
 Ring Flip:
Chair-Chair Conformational Change

Axial → Equatorial
Equatorial → Axial
A Conformational Analysis of a Cyclohexane:
1,3-Diaxial Interactions
❖ Substituted cyclohexane
• Two different chair forms

G
H
G
 less stable due to
1,3-diaxial interaction

❖ The larger the G group, the more severe the 1,3-

diaxial interaction and shifting of the equilibrium
from the axial-G chair form to the equatorial-G
chair form
 G

(equatorial) (axial) G

At 25oC
1,3-diaxial interaction
% of
G % of Axial
Equatorial
F 60 40
CH3 95 5
iPr 97 3
tBu > 99.99 < 0.01
Practice problem

Write a conformational structure for 1-

bromo-3-chloro-5-fluorocyclohexane in
which all the substituents are equatorial.
Then write its structure after a ring flip.

© 2014 by John Wiley & Sons, Inc. All rights reserved.

Disubstituted Cycloalkanes:
Cis-Trans Isomerism
H H H CH3

CH3 CH3 CH3 H

cis-1,2-Dimethyl trans-1,2-Dimethyl
cyclopropane cyclopropane
Cl Cl Cl H

H H H Cl
cis-1,2-Dichloro trans-1,2-Dichloro
cyclobutane cyclobutane
Cis-Trans Isomerism and Conformation
Structures of Cyclohexanes
❖ Trans-1,4-Disubstituted Cyclohexanes
more stable
UP Upper bond
CH3 H
ring H3C
4
1 H
H flip CH3
CH3 DOWN H
Lower bond
trans-Diaxial trans-Diequatorial
❖ Upper-lower bonds means the groups are trans
 ❖ Cis-1,4-Disubstituted Cyclohexanes

CH3 chair-chair CH3

ring H
H
H3C flip CH3
H H
Equatorial-axial Axial-equatorial
 ❖ Cis-1-tert-Butyl-4-methylcyclohexane

H3C
CH3
CH3 H3C
CH3 ring
H3C CH3
flip
H3C
(more stable (less stable
because large because large
group is group is
equatorial) axial)
❖ Trans-1,3-Disubstituted Cyclohexanes

(ax)
CH3
(eq) ring H H
H3C H flip
CH3
H CH3 (eq)
(ax)

trans-1,3-Dimethylcyclohexane
 ❖ Trans-1-tert-Butyl-3-methylcyclohexane
H3C
CH3
H3C
CH3 ring
H3C CH3
flip
H3C CH3
CH3
(more stable (less stable
because large because large
group is group is
equatorial) axial)
❖ Cis-1,3-Disubstituted Cyclohexanes

H
H ring
CH3
flip H H
CH3
CH3 CH3
(more stable) (less stable)
❖ Trans-1,2-Disubstituted Cyclohexanes

(ax)
(eq) CH3
CH3 ring
CH3 flip (ax)
(eq)
CH3
diequatorial diaxial
(much more stable) (much less stable)

trans-1,2-Dimethylcyclohexane
❖ Cis-1,2-Disubstituted Cyclohexane
(ax) (ax)
CH3
CH3
ring
CH3 flip CH3
(eq) (eq)
(equatorial-axial) (axial-equatorial)

cis-1,2-Dimethylcyclohexane
(equal energy and equally
populated conformations)
Practice problem

(a) Write the two conformations of cis-1-tert-

butyl-2-methylcyclohexane. (b) Which
conformer has the lower potential energy?

© 2014 by John Wiley & Sons, Inc. All rights reserved.

Practice problem

Write the structures of four chair

conformations of 1-tert-butyl-3-
methylcyclohexane. (b) Which conformation
is more stable?

© 2014 by John Wiley & Sons, Inc. All rights reserved.

Practice problem

Draw the possible conformations for the

following cyclohexane derivatives. Indicate
which conformer is the more stable.
Et
E t

t-B u
i-Pr

© 2014 by John Wiley & Sons, Inc. All rights reserved.

Chemical Reactions of Alkanes
❖ Alkanes are inert to many chemical reagents
o Strong C–C and C–H bonds
o C–H bonds are only slightly polarized

❖ Alkanes were originally called paraffins

(parum affinis, Latin: little affinity)
Synthesis of Alkanes and Cycloalkanes
Hydrogenation of Alkenes & Alkynes

H2
H H
Pt, Pd or Ni
C C
solvent
heat and pressure

2H2
H H
Pt, Pd or Ni
C C
solvent
heat and pressure H H
❖ Examples
Ni
+ H2
EtOH H H
o
25 C, 50 atm.

Pd H
+ H2
EtOH H
o
25 C, 1 atm.

Pd H H

EtOAc H H
+ 2 H2 o
65 C, 1 atm.
Practice problem

Write the structures of three pentenes

that would all yield pentane on
hydrogenation.

© 2014 by John Wiley & Sons, Inc. All rights reserved.

Practice problem

Show the reactions involved for

hydrogenation of all the alkenes and
alkynes that would
yield 2-methylbutane.

© 2014 by John Wiley & Sons, Inc. All rights reserved.

 Summary
❖ Nomenclature:
o Alkanes and cycloalkanes
o Alkyl halides
o Alcohols
o Alkenes and cycloalkenes
o Alkynes

❖ Bond rotation of sigma bonds:

o Sawhorse & Newman projection formulas
o Conformational analysis of ethane and butane
o The relative stabilities of cycloalkanes
o Conformational analysis of cyclohexane
• Axial and equatorial positions
• Cis-trans isomerism

❖ Synthesis of alkanes from alkenes and alkynes:

o Hydrogenation reaction