2.

Alkanes: Nature of
Organic Compounds

Mahmiah, S.Si., M.Si

Based on McMurrys Organic Chemistry, 7th edition

Why this Chapter
n Alkanes are unreactive, but provide useful vehicle to
introduce important ideas about organic compounds

n Alkanes will be used to discuss basic approaches to naming

organic compounds

n We will take an initial look at 3-D aspects of molecules

2
 2.1 Functional Groups
n Functional group -
collection of atoms at a site
that have a characteristic
behavior in all molecules
where it occurs

n The group reacts in a

typical way, generally
independent of the rest of
the molecule

n For example, the double

bonds in simple and
complex alkenes react with
bromine in the same way 3
Functional Groups with Multiple
CarbonCarbon Bonds
n Alkenes have a C-C
double bond
n Alkynes have a C-C
triple bond
n Arenes have special
bonds that are
represented as
alternating single
and double C-C
bonds in a six-
membered ring

4
Functional Groups with Carbon Singly
Bonded to an Electronegative Atom

5
Groups with a CarbonOxygen Double Bond
(Carbonyl Groups)

6
Survey of Functional Groups

7
Survey of Functional Groups

8
Survey of Functional Groups

9
Survey of Functional Groups

10
Problem : Identify the Functional Groups

11
2.2 Alkanes and Alkane Isomers
n Alkanes: Compounds with C-C single bonds and C-H
bonds only (no functional groups)
n Alkanes are often described as satured hidrocarbons
n Connecting carbons can lead to large or small molecules
n The formula for an alkane with no rings in it must be
CnH2n+2 where the number of Cs is n
n Alkanes are saturated with hydrogen (no more can be
added
n They are also called aliphatic compounds

12
A saturated fat (glyceryl stearate):

13
Alkanes structure

14
Alkane Isomers
n CH4 = methane, C2H6 = ethane, C3H8= propane
n The molecular formula of an alkane with more than
three carbons can give more than one structure
n C4 (butane) = butane and isobutane
n C5 (pentane) = pentane, 2-methylbutane, and 2,2-
dimethylpropane
n Alkanes with Cs connected to no more than 2 other
Cs are straight-chain or normal alkanes
n Alkanes with one or more Cs connected to 3 or 4 Cs
are branched-chain alkanes

15
Constitutional Isomers
n Isomers that differ in how their atoms are arranged in
chains are called constitutional isomers
n Compounds other than alkanes can be
constitutional isomers of one another
n They must have the same molecular formula to be
isomers

16
Condensed Structures of Alkanes
n We can represent an alkane in a brief form or in
many types of extended form
n A condensed structure does not show bonds but lists
atoms, such as
n CH3CH2CH2CH3 (butane)
n CH3(CH2)2CH3 (butane)

17
18
 Alkyl Groups
n Alkyl group remove
one H from an alkane (a
part of a structure)
n General abbreviation R
(for Radical, an
incomplete species or the
rest of the molecule)
n Name: replace -ane
ending of alkane with -yl
ending
n -CH3 is methyl (from
methane)
n -CH2CH3 is ethyl from
ethane
19
20
Types of Alkyl groups
n Classified by the connection site
n a carbon at the end of a chain (primary alkyl group)
n a carbon in the middle of a chain (secondary alkyl
group)
n a carbon with three carbons attached to it (tertiary alkyl
group)

R (alkyl group)
21
22
Example:
n Propose structure for two isomers C2H6O
- C : 4 bonds
- O : -O-H or C-O-C
- possible structure :

23
2.3 Naming Branched-Chain Alkanes
n Compounds are given systematic names by a process that uses

n Follows specific rules

n Find parent hydrocarbon chain
n Carbons in that main chain are numbered in sequence
n Substituents are identified numbered
n Write compound name is single word
n Name a complex substituents as though it were a compound
itself

24
1. Find the Parent: longest continuous carbon chain

25
2. Number the atoms in the chain

26
3. Identify &
number the
substituents

27
4. Write the name

28
 Rules for naming Branched Alkanes (or drawing
structure from name)
Find the longest chain and name it as a straight chain alkane
Name substituents as alkyl groups

Number the main chain starting from the end closest to a substituent
Write the name
Alphabetize by sub. (di-, tri-count only if part of sub. name)
Order #s from low to high; use smallest possible numbers
Capitalize the first letter only
Write as one word with commas and hyphens as needed
Complex substituents in parentheses

1
5-Ethyl-2,2-dimethyloctane 4-ethyl-3,6-dimethyldecane

1 1
1

5-(1,1-Dimethylethyl)-3-ethyloctane 4-(1-Ethylpropyl)-2,3-dimethylnonane
29
Practice : IUPAC name?

30
Solution:

31
 Practice : structure?
n3-isopropyl-2-methylhexane
nC-C-C-C-C-C
nTwo substituents: isopropyl &
methyl
nAdd hydrogens to complete the
structure

32
Solution:

33
Problem : IUPAC names?

34
Problem : Draw structures
1. 2-methylheptane
2. 4-ethyl-2,2-dimethylhexane
3. 4-ethyl-3,4-dimethyloctane
4. 2,4,4-trimethylheptane
5. 3,3-diethyl-2,5-dimethylnonane
6. 4-isopropyl-3-methylheptane

35
2.4 Properties of Alkanes
n Petroleum is a complex mixture of HK that must be
seperated into various fractions than refined before it
can be used

36
2.4 Properties of Alkanes
n Called paraffins (low affinity compounds) because
they do not react as most chemicals
n They will burn in a flame, producing carbon dioxide,
water, and heat

n They react with Cl2 in the presence of light to replace

Hs with Cls (not controlled)

37
Physical Properties
n Boiling points and melting points increase as size of
alkane increases
n Dispersion forces increase as molecule size
increases, resulting in higher melting and boiling
points

38
2.5 Conformations of Ethane
n Stereochemistry concerned with the 3-D
aspects of molecules
n bonds are cylindrically symmetrical
n Rotation is possible around C-C bonds in
open-chain molecules

39
Conformers
n Conformation- Different arrangement of
atoms resulting from bond rotation
n Conformations can be represented in 2 ways:

40
Torsional Strain
n We do not observe perfectly free rotation
n There is a barrier to rotation, and some
conformers are more stable than others
n Staggered- most stable: all 6 C-H bonds are
as far away as possible
n Eclipsed- least stable: all 6 C-H bonds are as
close as possible to each other

41
42
2.6 Drawing Chemical Structure
n A line between atoms: 2 electrones in covalent
bonding
n Drawing skeletal structures :
1. Carbon atoms ussually arent shown. A carbon
atoms is assumed to be at the intersection of two
lines (bonds) and at the end of each line.
2. Hydrogen atoms bonded to carbon arent shown.
3. All atoms other than C and H are shown

43
n Group: -CH3, -OH, and NH2 are ussually
written with C, O, or N atom first and the H
atom second. (H3C-; HO-; H2N-)
n If larger units such as CH2CH3 are not
inverted.

44
Problem:
n Convert the following skeletal structure into molecule structure
and tell how many H atoms are bonded to each carbon:

n Propose the skeletal structures from:

a. C4H8 b. C3H6O c. C4H9Cl

n Draw the skeletal structure :

PABA (sunscreens ingredients)

45
2.7 Cycloalkanes
n Satured cyclic HK are called cycloalkanes or
alicyclic (aliphatic cyclic).
n Formula : (CH2)n or CnH2n

46
Rules of naming Subtituted
Cycloalkanes
n Find the parent : count the number of C in the ring and the number of
the largest substituent chain.
C in the ring > substituent : alkyl-subtituted cycloalkane
C in the ring < substituent : cycloalkane- subtituted alkyl.

n Number the substituents and write the name

47
48
Problem
n Give IUPAC names :

n Draw the structures:

a. 3-Cyclopropylhexane
b. 1-Ethyl-4-isopropylcyclohexane

49
2.8 Cis-Trans Isomerism in Cycloalkanes
n Similar to acyclic alkanes
n Less flexible rotation or rigid, planar molecule

n Cycloalkanes : two side atop and a bottom side

Cis and trans isomers
cis = alkyl/FG on the same side of the ring
trans = alkyl/FG on the opposite side of the ring

50
Example :
n Name the following substances including cis or trans
prefix :

Answer:
a. trans-1,3-Dimethylcyclopentane
b. cis-1,2-Dichlorocyclohexane

51
Problem:
n Draw both cis and trans isomers of:
a. 1,2-Dibromocyclobutane
b. 1,3-Dimethylcyclopentane
n Name the following substances: (red : Br)

52
2.9 Conformations of Some Cycloalkanes

n Cycloprapane, Cyclobutane, and Cyclopentane

Cyclopropane is a planar (angle strain); C-H bond an
eclipsed
Cyclobutane, and Cyclopentane slightly puckered

53
2.9 Conformations of Some Cycloalkanes

n Cyclohexane
Chair conformation not flat/planar

54
2.9 Conformations of Some Cycloalkanes

n Cyclohexane
all C-C-C bond angles are near 109, C-H
bond are staggered

55
Cyclohexane
n A chair conformation is drawn in 3 steps:

56
2.10 Axial and Equatorial Bond in Cyclohexane

n Axial positions: perpendicular to the ring, paralel to

the ring axis
n Equatorial positions: in the rough plane around the
ring equator

57
n A prosedure for drawing axial and equatorial
bonds in cyclohexane

58
2.11 Conformational Mobility of Cyclohexane

n ring flip of a chair cyclohexane

n Methylcyclohexane: the equatorial conformation is more stable

than axial conformation steric strain

59
n Drawing 1,1-Dimethylcyclohexane in a chair
conformation

60
Take Home Exams:

n Answer the question at page 72-77

61