ORGANIC CHEMISTRY 1

LU 3: ALKANE

Nomenclature, Conformational Analysis, and

an Introduction to Synthesis
 OUTLINE
Part 1:- Nomenclature (IUPAC)
Alkane
Alkyl halide
Alcohol
Cyclohexane & bicyliccompounds
Part 2:- Reaction of alkane
Hydrogenation (=, ≡  - )
Grignard reagent (RMgX  -)
Alkylation of Terminal Alkynes (R≡H  -)
Decarboxylation of salts of carboxylic acids (ROOH  -)

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Revision
Shapes of Alkanes
 “Straight-chain” alkanes have a zig-zag orientation when they are in their
most straight orientation
 Straight chain alkanes are also called unbranched alkanes

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 Branched alkanes have at least one carbon which is attached to more than two
other carbons

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Constitutional isomers
 Constitutional isomers have the same molecular formula but different
connectivity of atoms
 Different physical properties (melting point, boiling point, densities etc.)
 Boiling point of branching alkane less- compound more compact & less surface
area, intramolecular forces depend on surface area. Weak intermolecular forces

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 The number of constitutional isomers possible for a given molecular
formula increases rapidly with the number of carbons

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NOMENCLATURE OF ALKANE

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 IUPAC - Nomenclature

 Before the end of the 19th century compounds were named using
nonsystematic nomenclature
 These “common” or “trivial” names were often based on the source of
the compound or a physical property
 The International Union of Pure and Applied Chemistry (IUPAC)
started devising a systematic approach to nomenclature in 1892
 The fundamental principle in devising the system was that each
different compound should have a unique unambiguous name
 The basis for all IUPAC nomenclature is the set of rules used for
naming alkanes

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Nomenclature of Unbranched Alkanes
(Straight-chain)

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Nomenclature of branched Alkyl groups
 The branched alkyl groups are obtained by removing one hydrogen from
the alkane and named by replacing the -ane of the corresponding alkane
with -yl

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 Naming Alkanes -IUPAC
 Step 1: Locate the longest continuous chain of carbons  parent chain and
determines the parent name.

 Step 2: Identify and name the substituent group attached to parent chain
 Step 3: Number the longest continuous chain in the direction that gives the lowest
number to the substituent group

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 When two or more substituents are identical,
identical use the prefixes di-, tri-, tetra- etc.
 Commas are used to separate numbers from each other
 The prefixes are used in alphabetical prioritization
 When two chains of equal length compete to be parent, choose the chain with the
greatest number of substituents

 Choose the name that gives the lower number at the first point of difference

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COMMON NAMES FOR
BRANCHED CHAIN FOR
ALKYL GROUP

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Example:

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 Practice Questions

5-Ethyl-2,4,6-trimethyloctane

4-ethyl-2-methylhexane

3-isopropyl-2-methylhexane
Conformation of Ethane

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Conformational Analysis  Sigma Bonds and Bond Rotation
 Ethane has relatively free rotation around the carbon-carbon bond

 These two hydrogen atoms appear to be separated by an angle of 60°. This angle is
called the dihedral angle or torsional angle.
 Possible confirmation: The staggered conformation is the lowest in energy, while the
eclipsed conformation is the highest in energy.

*dihedral angle
changes as the
C−C bond rotates

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 The staggered conformation has C-H bonds on adjacent carbons as far apart from each
other as possible

 The eclipsed conformation has all C-H bonds on adjacent carbons directly on top of
each other

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 The potential energy diagram of the conformations of ethane

 The staggered conformation is more stable than eclipsed by 12 kJ mol-1

 Different in energy referred to as Torsional strain  repulsion by the bonding
e- of one substituent to the bonding e- of another substituent.

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Conformational of other alkanes - Butane

 Rotation around C2-C3 of butane gives six important conformations

 The gauche conformation is less stable than the anti conformation by 3.8 kJ
mol-1 because of repulsive van der Waals forces between the two methyl.
 Called a gauche interaction, is a type of steric interaction (strain) 
repulsion between the e- clouds of atoms or groups that are too close to each
other.
Nomenclature of Alkyl Halides (R-X)

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 Alkyl halide?
Alkyl halide- carbon atom, which bonded to the halogen(X).

X = F, Cl, Br, I

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In IUPAC nomenclature halides are named as substituents on the parent chain
 Halo and alkyl substituents are considered to be of equal ranking

In common nomenclature the simple haloalkanes are named as alkyl halides
Common nomenclature of simple alkyl halides is accepted by IUPAC and still used

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 Alkyl halides are classified as:
 Primary halide – the halogen bearing C is bonded to 1 C atom.
 Secondary halide - the halogen bearing C is bonded to 2 other C
atoms.
 Tertiary halide - the halogen bearing C is bonded to 3 other C
atoms.
R'
R'
R C X
R CH2 X R CH X
R"
1 alkyl halide
o
2 alkyl halide
o
3o alkyl halide

Br
CH3CH2CH2 Cl (CH3)3C Cl
CH3 CH CH2CH3 2-chloro-2-
1-chloropropane
2-bromobutane methylpropane

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 Recall THE RULE:
1. Identify and name the parent.
2. Identify and name the substituents.
3. Number the parent chain and assign a locant to each substituent – lowest
position
4. Assemble the substituents alphabetically

 Alkyl Halide  Halogens are simply treated as substituents and

receive the following names: fluoro-, chloro-, bromo-, and iodo

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Nomenclature of Alcohol (R-OH)

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 Common Names of simple alcohols are still often used and are approved by
IUPAC

 Alcohols with two hydroxyls are called diols in IUPAC nomenclature and
glycols in common nomenclature

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NOMENCLATURE OF
CYCLOALKANES

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Nomenclature of Cycloalkanes
 The prefix cyclo- is added to the name of the alkane with the same number of
carbons
 Rules:
1. When one substituent is present it is assumed to be at position one
and is not numbered

2. When two alkyl substituents are present the one with alphabetical
priority is given position 1

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 Rules:
3. Numbering continues to give the other substituent the lowest number

4. Hydroxyl has higher priority than alkyl and is given position 1

5. If a long chain is attached to a ring with fewer carbons, the cycloalkane is

considered the substituent

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 Rules:

6.If more than one cyclic ring attached to a side chain, the cycloalkane
is considered the substituent irrespective to the number of carbon atom
in the ring or chain

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Cyclic system in cycloalkane  Bicyclic compounds
 Bicyloalkanes contain 2 fused or bridged rings
 The alkane with the same number of total carbons is used as the parent and
the prefix bicyclo- is used

 The number of carbons in each bridge is included in the middle of the

name in square brackets – in descending order

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 HOW TO NAME BICYCLIC
COMPOUNDS
Example:-
H3C

1. Identify the carbon bridge H3C

1 1
1
2 2
2. Identify carbon on each side and carbon at the bridge H3C
3
3 2
4

3. Name the cyclic system

Total carbon in ring
Bicyclo [4,3,0] nonane 2
9 1
in descending order 3
H3C
8
4
4. For substituent, numbering the bicyclic need to start 7
6
5
with the larger ring to small ring
8MethylBicyclo[4,3,0]nonane 35
CONFORMATION OF
CYLOHEXANE

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 Substituted Cyclohexane: Axial and Equatorial Hydrogen Atoms

 Axial hydrogens are perpendicular to the average plane of the ring

 Equatorial hydrogens lie around the perimeter of the ring
 The C-C bonds and equatorial C-H bonds are all drawn in sets of parallel lines
 The axial hydrogens are drawn straight up and down

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 Methyl cyclohexane is more stable with the methyl equatorial
 An axial methyl has an unfavorable 1,3-diaxial interaction with axial C-H
bonds 2 carbons away
 A 1,3-diaxial interaction is the equivalent of 2 gauche butane interactions

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Disubstituted Cycloalkanes
 Can exist as pairs of cis-trans stereoisomers
 Cis: groups on same side of ring
 Trans: groups on opposite side of ring

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 Trans-1,4-dimethylcylohexane prefers a trans-diequatorial conformation

 Trans is more stable due to

equatorial conformation of
both methyl groups.
 Proved by heat of combustion

 Cis-1,4-dimethylcyclohexane exists in an axial-equatorial conformation

 The most stable conformation has larger substituent in an equatorial orientation

 A very large tert-butyl group is required to be in the more stable equatorial position

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Physical Properties of Alkanes and Cycloalkanes
 Boiling points of unbranched alkanes increase smoothly with number of
carbons

 Melting points increase in an alternating pattern according to whether the

number of carbon atoms in the chain is even or odd

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Reaction of Alkane
Preparation Alkane
-Hydrogenation (Alkenes and alkynes)
-Grignard reagent
-Alkylation of Terminal Alkynes
-Decarboxylation of salts of carboxylic acids

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Synthesis of Alkanes

Hydrogenation of Alkenes and Alkynes

addition of molecular hydrogen (H2) across a double bond in the presence of
a metal catalyst

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Grignard Reaction
 Prepared from organic halides by reaction with magnesium (Mg) (Grignard
reagent) in the presents of dry ether.

 Grignard reagents are carbon nucleophiles capable of attacking a wide range of

electrophiles  carbanions
 Hydrolyzed by water or acid to form alkanes

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Decarboxylation of salts of carboxylic acids
 The loss of a molecule of carbon dioxide from a carboxylic acid.

 Carboxylic acid with NaOH forms Na salt of carboxylic acid.

R-COOH + NaOH → R-COONa + H2O

 On heating with soda lime, it yields alkanes

R-COONa + NaOH → R-H + Na2CO3

Example: CH3-COOH + NaOH → CH3-COONa + H2O

Ethanoic acid Sodium ethanoate

CH3-COONa + NaOH → CH4 + Na2CO3

methane

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Alkylation of Terminal Alkynes
 Alkynes can be subsequently hydrogenated to alkanes

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LET’S CONTINUE NEXTWEEK!!