Chapter 2

The Nature of Organic Compounds:

Alkanes
 Functional Groups

• The structural features that make it possible to

classify compounds by reactivity are called
functional groups
• A given functional group behaves almost the same
way in every molecule it’s a part of.
• Functional group is a group of atoms within a
molecule that has a characteristic chemical
behavior
Ethylene –
plant
hormone
that causes
Menthene – a
fruit to
ripen molecule
found in
peppermint oil
Carbon-Carbon Multiple bonds
Carbon singly bonded to an electronegative atom
Carbon-Oxygen Double Bond (carbonyl groups)
(-al) (-one) (-oic acid)
 Classifying Organic Compounds

Functional groups are group of atoms (or one atom) that

have specific behavioral characteristics in organic
compounds.
Organic compounds are classified based on the functional
groups that they contain.

12
 Classifying Organic Compounds

The list of common

functional groups
found in organic
compounds are
shown here on
Table 19.1.

13
 Classifying Organic Compounds

The list of important functional groups found in

biological compounds is shown here on Table 19.2.

14
 Classifying Organic Compounds

Ethanol contains the alcohol functional group and dimethyl

ether contains the ether functional group. They have the
same molecular formula but the boiling point (b.p.) of
ethanol is 78C while the b.p. of dimethyl ether is -23C
because of the structural differences between the
molecules. 15
 Organic Formulas and
Molecular Models
Structural formulas or models are often used in organic
chemistry to illustrate molecules.

For example,

or in the case of a model.

16
Figure 19.3 Types of formulas and models used to represent
organic molecules. Each diagram is a representation of a
propane molecule.

17
 Organic Formulas and Molecular Models
This is an example of how to change a condensed structural
formula into a line structure.

The table on the next slide summarize formulas and

models used in organic chemistry. 18
 Formula or model Definition
Lewis structure Shows all bonds, all atoms, and all nonbonding
electrons
Structural formula Same as Lewis structure except nonbonding
electrons are not shown

Bonds are collapsed so relative positions

Condensed structural formula of atoms are group together

Only bonds and functional groups are shown and

Line structure each endpoint and bend represents a carbon atom

Atoms are shown as balls and bonds as sticks

Ball-and-stick model and the shape is shown at the central atom.

Bonds are omitted and the size of atoms are

Space-filling model emphasized.
19
 Alkanes and Alkyl Groups: Isomers

• Hydrocarbon: a compound composed only of carbon

and hydrogen
• Saturated hydrocarbon: a hydrocarbon containing
only single bonds
• Alkane: a saturated hydrocarbon whose carbons are
arranged in an open chain
– General molecular formula, CnH2n+2
– Homologous series, -CH2- (methylene) group
• Aliphatic hydrocarbon: another name for an alkane
 Hydrocarbons
Hydrocarbons are organic compounds that contain only
carbon and hydrogen atoms. (e.g. propane, CH3CH2CH3
is a hydrocarbon but ethanol, CH3CH2OH is not).

Hydrocarbons are classified as either aliphatic (i.e those

hydrocarbons without benzene rings in the chemical
structure) or aromatic.(i.e those hydrocarbons with
benzene rings in the chemical structure) as shown in
Figure 19.4 on the next slide.

Hydrocarbons are also classified as saturated or unsaturated

compounds. 21
Figure 19.4 Classes of Hydrocarbons

22
 Hydrocarbons

The principal source of hydrocarbons is fossil fuels which

include natural gas, petroleum, and coal.

Fossil fuels are the primary source of heat and also a

primary source of organic chemicals.

23
 Isomerism

Because carbon can form four single bonds, alkanes with

four or more carbon atoms can form isomers.

Isomers are molecules that have the same molecular formula

but different structural formula.

25
Constitutional Isomerism
• Constitutional isomers: compounds with the
same molecular formula but a different
connectivity (order of attachment of their
atoms)
• Molecular formula Constitutional isomers
CH4 1
C2H6 1
C3H8 1
C4H10 2
C5H12 3
C10H22 75
C15H32 4347
• Straight-chain alkanes (normal (n) alkanes)
– n-butane
• Branched-chain alkanes
– Isobutane (2-methylpropane)
 Your Turn!

There are several isomers of heptane, C7H16. Draw

structural formulas and condensed structural
formulas for the two isomers that only have one
branching methyl group.

30
Substituent group CnH2n + 1
Alkyl groups (R-); suffix -yl
Classification of C & H
Primary (1°) C: a carbon bonded to one other carbon
– 1° H: a hydrogen bonded to a 1° carbon
Secondary (2°) C: a carbon bonded to two other carbons
– 2° H: a hydrogen bonded to a 2° carbon
Tertiary (3°) C: a carbon bonded to three other carbons
– 3° H: a hydrogen bonded to a 3° carbon
Quaternary (4°) C: a carbon bonded to four other carbons
R – generalized alkyl group (e.g. methyl, ethyl, Rest of the
molecule which isn’t specified)
 Your Turn!

Pyridoxal Phosphate, a close relative of Vitamin B6, is

involved in a large number of metabolic reactions. Classify
the carbons in its structure as 10, 20, or 30
 Naming Branched-chain Alkanes

IUPAC system of nomenclature

(International Union of Pure and Applied Chemistry)
 Naming Branched-chain Alkanes
• Step1 Find the parent hydrocarbon
1. Find the longest continuous carbon chain in
the molecule

2. If two chains of equal length are present,

choose the one with the larger number of
branch points as the parent
• Step1 Find the parent hydrocarbon
• Step2 Number the atoms in the main chain
– If there is one substituent, number from the end
of the chain that gives it the lower number
– If more than one substituents is attached to the
longest continuous chain, the chain number in
the direction that will result in the lowest
possible number
• Step1 Find the parent hydrocarbon
• Step2 Number the atoms in the main chain
• Step3 Identify and number the substituents
– Assign a number to each substituent according to its
point of attachment on the parent chain
– If there are two substituents on the same carbon, assign
them both the same number
 Naming Branched-chain Alkanes
• Step1 Find the parent hydrocarbon
• Step2 Number the atoms in the main chain
• Step3 Identify and number the substituents
• Step4 Write the name as a single word
– Use hyphens to separate the various prefixes and
commas to separate numbers
– If two or more different side chains are present, cite
them in alphabetical order
– If two or more identical side chains are present, use one
of the di-, tri-, tetra-, and so forth. Don’t use these
prefixes for alphabetizing
 Nature of Carbon-Carbon
Infix Bonds in the Parent Chain
-an- all single bonds
-en- one or more double bonds
-yn- one or more triple bonds

Suffix Class
-e hydrocarbon
-ol alcohol
-al aldehyde
-one ketone
-oic acid carboxylic acid
 Properties of Alkanes
Physical Properties
• Low-molecular-weight alkanes
(methane....butane) are gases at
room temperature
• Higher-molecular weight
alkanes (pentane, decane,
gasoline, kerosene) are liquids
at room temperature
• High-molecular weight alkanes
(paraffin wax) are semisolids or
solids at room temperature
 Dispersion force

Intermolecular forces of attraction

• Ion bonding (188 kcal/mol)
• Hydrogen bonding (2-10 kcal/mol)
• Dispersion force (0.02-2 kcal/mol)
 Physical properties
Constitutional isomers have different physical properties

• Constitutional isomers have different physical

properties
mp bp Density
Name (°C) (°C) (g/mL)
hexane -95 68.7 0.659
2-methylpentane -154 60.3 0.653
3-methylpentane -118 63.3 0.664
2,3-dimethylbutane -129 58.0 0.661
2,2-dimethylbutane -98 49.7 0.649
bp: more branch, lower
mp: branch, decrease; but symmetry, increase
• Reactions of alkanes:
– The reaction of an alkane with O2 occurs during
combustion in an engine or furnace when the
alkanes is used as a fuel
– Carbon dioxide and water are formed as
products, and a large amount of heat is released
CH4 + 2 O2 → CO2 + 2 H2O + 890 KJ
(213 Kcal)
 Conformations of Ethane
• The 3-dimentional (3D)arrangements of atoms
that result from rotation around a single bond are
called conformations
• They interconvert too rapidly for them to be
isolated
 (99%) (1%)

• Staggered conformation: a conformation about a carbon-

carbon single bond where all six C-H bonds are as far
away from one another as possible
• Eclipsed conformation: a conformation about a carbon-
carbon single bond where the six C-H bonds are as close
as possible
• Torsional strain (~12 KJ/mol)
(2.9kcal/mol)
Decane
Drawing Chemical Structures
Skeletal Skeletal
structure structure

▪Carbon atoms usually aren’t

shown
▪Hydrogen atoms bonded to
carbon aren’t shown
▪All atoms other than carbon
and hydrogen are shown.
 Cycloalkanes
• General formula: (CH2)n or CnH2n
Step 1 Find the parent chain

Step 2 Number the substituents, and write the

name
 Cis-Trans Isomerism in Cycloalkanes

• Cycloalkanes are less flexible than the

open-chain alkanes
• No rotation around a C-C bond can take
place in cycloalkane without breaking the
ring
• Because of their cyclic structure,
cycloalkanes have two sides: a “top”side
and a “bottom”side
• Isomerism is possible in substituted
cycloalkanes
• Constitutional isomers
– Have different connections among atoms
• Stereoisomers
– Have the same connections
– Differ in three-dimensional orientation
• Cis-trans isomers have
– a subclass of stereoisomers
– the same molecular formula
– the same connectivity
– an arrangement of atoms in space that cannot be
interconverted by rotation about single bonds under
ordinary conditions
• Cis: A prefix meaning on the same side
Trans: A prefix meaning on opposite side
 Conformations of Some Cycloalknes

• Cyclopropane
– is a flat, triangular molecule with C-C-C bond
angles of 60o
– All six C-H bonds have an eclipsed arrangement
with their neighbors
• Intramolecular strain:
– Torsional strain: arises when atoms not bonded
to each other are forced abnormally close to
each other; e.g., eclipsed hydrogens in ethane
– Angle strain: introduced into a molecule when
a bond angle is deformed from its ideal value
(109.5o)
– Steric strain: arises when two groups are too
close together and try to occupy the same space
• Cyclohexane
– is a not flat
– All C-C-C bond angles are near 109o
– All adjacent C-H bonds are staggered
– Three-dimensional shape called a chair
conformation
Axial and Equatorial Bonds in
Cyclohexane
 Axial and Equatorial Bonds in
Cyclohexane
• There are two kinds of positions for
hydrogens on the chair conformation of
cyclohexane
– Axial position is perpendicular to the ring
– Equatorial position is in the plane of the ring
• Each carbon atom has one axial and one
equatorial position
• Each side of the ring has 3 axial and 3
equatorial positions
Conformational mobility of Cyclohexane

• There are two equivalent chair

conformations
• Different chair cyclohexane conformations
readily interconvert, resulting in the
exchange of axial and equatorial positions
– all C-H bonds equatorial in one chair are axial in
the other, and vice versa
• For monosubstituted cyclohexane, the substituent is
always more stable in an equatorial position than in
an axial position
• A steric interference occurs in the axial
conformation in methylcyclohexane
• The 1,3-diaxial interaction introduces 7.6 kJ/mol of
steric strain into the methylcyclohexane because the
axial methyl group and the nearby axial hydrogen
are too close together
(1,3-diaxial interaction) (more stable)