Lecture 5

ALKANES, CYCLOALKANES AND

THEIR STEREOCHEMISTRY

Organic chemistry, John McMurry

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ALKANES, CYCLOALKANES AND THEIR STEREOCHEMISTRY

• Prefixes 1o, 2o, 3o, 4o

• Alkanes
• Isomer
• Chapter 5 Reading:
• Naming • Alkanes: 3.2 (isomer), 3.3 (Alkyl), 3.4
• Properties (name), 3.5 (properties), 3.6, 3.7
• Conformation (Conformation)
• Cycloalkanes • Cylcloalkanes: 4.1 (name), 4.2 (cis-
• Naming trans isomer), 4.3 (ring strain), 4.4-4.9
• Conformation (conformation)

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Primary, secondary, tertiary and
quaternary Carbon

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 Primary, secondary, tertiary and
quaternary Alcohol and Alkyl halide

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Primary, secondary, tertiary and
quaternary Amine and Amide

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Alkanes

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 Alkane Isomers
• Formula CnH2n+2

• Only single (sigma) bond, described

as saturated hydrocarbons
(alipha3c compounds)

• Isomers differ in how their atoms

are arranged in chains: straight-
chain and branch-chain

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Constitutional Isomers

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Alkyl Groups
• Remove 1 H atom: Free radical, not stable compounds
• To call a group as a part of compound: –ane (alkane) ! –yl (alkyl)

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Nomenclature
International Union of Pure and Applied Chemistry
(IUPAC) system of nomenclature

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 Naming Steps
1. Find parent hydrocarbon chain
The longest continuous chain,
with the most branches

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Naming Steps
2. Number the atoms in the longest chain: so that the
sum of locant numbers is minimum

OR

OR

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Naming Steps
3. Naming
• Substituent: alkyl
• Same group at different position: add di, tri, tetra,…
• Use hyphen “-” to separate number-let t er,
use comma “,” to separate number-number
• Write the name as a single word

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Naming Steps
3. Naming
• Substituent: alkyl
• Same group at different position: add di, tri, tetra,…
• Use hyphen “-” to separate number-lee er,
use comma “,” to separate number-number
• Write the name as a single word

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Naming Steps
Name a branched substituent as though it were itself a
compound

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Example
Give IUPAC names for the following compounds:
a)

b)

c)

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Properties of Alkanes
• Called paraffins because they do not react as most
chemicals
• Low affinity compounds
• Burn in a flame, producing carbon dioxide, water, and
heat
• Methane reacts with Cl2 in the presence of light to
produce:

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 Physical Properties of Alkanes
• Boiling points and melting points increase as size of alkane increases
• Dispersion forces increase as molecule size increases, resulting in
higher melting and boiling points

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 Conformations
• Stereochemistry: Branch of chemistry concerned with the 3D
aspects of molecules
• Rotation is possible around C–C SINGLE bonds in open-chain
molecules

• Conforma3on: Different arrangement of atoms resulting

from bond rotation

Can be represented in 2 ways

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Torsional Strain
• Perfectly free rotation is not observed
• There is a barrier to rotation, and some conformers are
more stable than others
• Staggered conforma3on: Most stable
• All 6 C–H bonds are as far away as possible
• Eclipsed conforma3on: Least stable
• All 6 C–H bonds are as close as possible to each other
• Strain in a molecule caused by electron repulsion
between eclipsed bonds (can be released by bond
rota.on) ! Torsional strain

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A Graph of Potential Energy Versus Bond
Rotation in Ethane

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 Conformations of Propane

Conformations of Butane

An3 conforma3on: Geometric arrangement

around a C–C single bond in which the two
largest substituents are 180°apart 22
 Conformations of Butane
" Not all staggered conformations have same energy
" Not all eclipsed conformations have same energy

Gauche conforma3on: Conformation of butane in which the

two methyl groups lie 60°apart

Steric Strain: caused by the repulsion

between bulky groups

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A Plot of Potential Energy Versus Rotation
for the C2–C3 Bond in Butane

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Energy Costs for Interactions in
Alkane Conformers

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Example
• Sight along the C2–C3 bond
of 2,3-dimethylbutane
• Draw a Newman projection of the most stable
conformation
• Solution:

• This conformation of 2,3-dimethylbutane is the most

stable because it is staggered
• Has the fewest CH3↔CH3 gauche interactions

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 Summary
• Alkanes don’t contain functional groups, are relatively inert,
and can be either straight-chain or branched
• Constitutional isomers are compounds that have the same
chemical formula but different structures which differ in
their connections between atoms
• Rotation is possible around σ bonds because of their
cylindrical symmetry
• Alkanes exist in a large number of rapidly interconverting
conformations
• Newman projections make it possible to visualize the spatial
consequences of bond rotation
• Generally all alkanes are most stable when all of its bonds
are staggered
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Cycloalkanes

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Cycloalkanes
• Cycloalkanes or alicyclic compounds: Saturated cyclic
hydrocarbons
• General formula (CnH2n)

skeletal drawings
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Naming Cycloalkanes
• Find the parent
• Count the number of carbons in the ring
• Count the number in the largest substituent

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Naming Cycloalkanes
• Number the substituents
• Write the name

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Example
• Give IUPAC names for the following cycloalkanes

a)

b)

di, tri, tetra, sec, tert: not count in naming order

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 Cis-Trans Isomers
• Cycloalkanes are less flexible than open-chain alkanes
• Significantly lesser conformational freedom in cycloalkanes

• With the ring: isomerism is possible in substituted cycloalkanes

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Cis-Trans Isomers
• Cis-trans isomers: Stereoisomers that differ in their
stereochemistry about a ring or double bond
• Common occurrence in substituted cycloalkanes and
several cyclic biological molecules

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Example
• Draw the structures of the following molecules:
• a) trans-1-Bromo-3-methylcyclohexane
• b) cis-1,2-Dimethylcyclobutane
• Solution:

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Ring Strain
• Steric strain - Caused due to repulsive interactions when
atoms approach each other too closely
• Torsional strain - Caused due to eclipsing of bonds
between neighboring atoms
• Angle strain: Induced in a molecule when bond angles are
forced to deviate from the ideal 109° tetrahedral value

! n on-planar ring to minimize angle strain and torsional

strain
• Larger rings have many more possible conformations than
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smaller rings
Example
• Each H ↔ H eclipsing interaction in ethane costs about 4.0
kJ/mol
• How many such interactions are present in
cyclopropane?
• What fraction of the overall 115 kJ/mol (27.5 kcal/mol)
strain energy of cyclopropane is due to torsional strain?

• Solution:

• Hydrogen atoms on the same side of the cyclopropane

ring are eclipsed by neighboring hydrogens
• Six eclipsing interactions, three on each side of the ring
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Example

• Cost of six interactions = 4.0 kJ/mol ×6

= 24.0 kJ/mol
• Percentage of total strain energy of cyclopropane
24 kJ/mol
due to torsional strain = × 100%
115kJ/mol

= 21 %

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 Conformations of Cyclopropane

C–H bonds are eclipsed

! Has considerable torsional strain

Most strained of all rings

(C–C–C angles of 60°),
bent bonds

Cyclopropane bonds are weaker and more reac3ve than alkane’s

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Conformations of Cyclobutane
• If it was planar:
• Has less angle strain than cyclopropane
• More torsional strain because of larger number of ring
hydrogens, and their proximity to each other
• In fact: slightly bent out of plane, one carbon atom is
about 25°above the plane
• ! Increases angle strain but decreases torsional
strain

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 Conformations of Cyclopentane
• If it was planar:
• No angle strain
• Large torsional strain
• Non planar:
• Four carbon atoms are approximately in the same plane
• Fiv h carbon atom is bent out of the plane
! balance: increased angle strain & decreased torsional strain

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Example
• Two conformations of cis-1,3-dimethylcyclobutane
are shown
• What is the difference between them?
• Which one is likely to be more stable?

The methyl groups are farther apart in the more stable conformation
of cis-1,3 dimethylcyclobutane
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Conformations of Cyclohexane
• Occur widely in nature
• Adopts chair conformation
• Chair conforma3on: Strain-free, three-dimensional shape
• Has neither angle strain nor torsional strain

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Draw Cyclohexane Chair Conformation

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Alternate Conformation of Cyclohexane
• Boat cyclohexane:
• No angle strain
• Large number of eclipsing interactions

• Twist-boat conforma3on:
• More stable than a pure boat conformation
• Nearly free of angle strain

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 Axial and Equatorial Bonds
in Cyclohexane
• Chair cyclohexane has:
• 6 Axial hydrogens perpendicular to the ring
• 6 Equatorial hydrogens near the plane of the ring

• Chair conformation positions for substituents on the

ring
• Axial positions
• Equatorial positions

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Drawing Axial and Equatorial Bonds

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Ring-flip
Interconversion of chair conformations, resulting in
the exchange of axial and equatorial positions

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 Conformations of Monosubstituted
Cyclohexanes
• Rapidly flips at room temperature
• Two conformations aren’t equally stable
• Equatorial conformer > the axial by 7.6 kJ/mol
• (e) is more stable than (a)

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Steric Strain in Monosubstituted
Cyclohexanes

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Example
• What is the energy difference between the axial
and equatorial conformations of cyclohexanol
(hydroxycyclohexane)?
• Solution:
• An axial hydroxyl group causes 2 x 2.1 kJ/mol of steric
strain (From Table 4.1)
• Energy difference between axial and equatorial
cyclohexanol is 4.2 kJ/mol

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Conformations of
Disubstituted Cylcohexanes
• Cis isomer
• Both methyl groups are on the same face of the ring
• Compound can exist in two chair conformations

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 Conformations of
Disubstituted Cylcohexanes
• Trans isomer
• Methyl groups are on opposite faces of the ring

• Mostly in (e,e) conformation; only a gauche butane

interaction between methyls (3.8 kJ/mol)

• In (a,a) conformation: four 1,3-diaxial interactions

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 Example
• Draw two different chair conformations of
trans-1,4-dimethylcyclohexane
• Label all positions as axial or equatorial

• Solution:

• Methyl substituents are either both axial or both equatorial

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Example
• Draw the more stable chair conformation of the
following molecules
• Estimate the amount of strain in each
• a) trans-1-Chloro-3-methylcyclohexane
• b) cis-1-Ethyl-2-methylcyclohexane
• Solution:
• a) trans-1-Chloro-3-methylcyclohexane

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 Example
• b) cis-1-Ethyl-2-methylcyclohexane

• 1 CH3 ↔ CH2CH3 gauche = 3.8 kJ/mol

• 2 (H–CH2CH3) = 8.0 kJ/mol
• Total = 11.8 kJ/mol • 1 CH3 ↔ CH2CH3 gauche = 3.8 kJ/mol
• 2 (H–CH3) = 7.6 kJ/mol
• Total = 11.4 kJ/mol

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Summary
• Cycloalkanes are saturated cyclic hydrocarbons
with the general formula CnH2n
• Not all cycloalkanes are equally stable
• Three kinds of strain contribute to the overall
energy of a cycloalkane: Angle strain, torsional
strain, and steric strain
• Disubstituted cycloalkanes can exist as cis-trans
isomers

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Summary
• Cyclohexane adopts a puckered chair conformation
and hence is strain free
• Chair cyclohexanes have two positions: Axial and
equatorial
• Chair cyclohexanes are conformationally mobile
and are capable of undergoing a ringflip
• Axial substituents cause 1,3-diaxial interactions
making substituents on the ring more stable in the
equatorial position

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HW
• Alkanes:
• Naming: 3.12 and 3.14, 3.38, 3.40
• Isomer: 3.23, 3.24
• Newman projection: 3.42, 3.43, 3.51
• Cycloalkanes:
• Conformation: 4. 36, 4.49, 4.51, 4.53

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