Alkanes and

Cycloalkanes
Structure Forms
Kekulé or
Wedge/dash

C 3H 8 H3C CH2 CH3 H H

H H
skeletal
CH3CH2CH3 H H H
condensed H

2
Classes of Hydrocarbons
Organic Compounds

hydrocarbons (C,H) heteroatomic (O, N, P, S, X, etc.)

aliphatic (fatty) aromatic (pleasant smelling)

alkane alkene alkyne cyclic

C C C C C C

3
Functional Groups
⚫ A functional group is an atom or group of atoms that have a
characteristic chemical behavior.
⚫ The chemistry of every organic molecule, regardless of size and
complexity, is determined by the functional groups it contains.

4
Functional Groups

O
C
H3 C O O
C H
O

5
Types of Functional Groups:
Multiple Carbon–Carbon Bonds
⚫ Alkenes have a C-C
double bond
⚫ Alkynes have a C-C
triple bond
⚫ Arenes have
special bonds that
are represented as
alternating single
and double C-C
bonds in a six-
membered ring
6
Functional Groups
⚫ Alkyl halide

H H H H
H C C C C Br
H H H H

R-X where X is any “halogen”

7
Functional Groups
⚫ Alcohols

H H H H
H C C C C OH
H H H H

R-OH where R is any “alkyl group”

8
Functional Groups
⚫ Ethers

H H H
H C C O C H
H H H

R-O-R’ where R is any “alkyl group”

9
Functional Groups
⚫ Aldehydes

H O
H C C H
H
10
Functional Groups
⚫ Ketone

H O H
H C C C H
H H
Propanone (acetone)

11
Functional Groups
⚫ Carboxylic acids

H O
H C C OH
H
Ethanoic acid (acetic acid)

12
Functional Groups
⚫ Ester

H O
H C C O CH3
H
Methyl ethanoate
(methyl acetate)
13
Functional Groups
⚫ Amine
H
H C NH2
H
Methylamine

14
Functional Groups
⚫ Amide

O
H3 C C NH2
Ethanamide (acetamide)

15
Functional Groups
⚫ Acid anhydride

O O
H3 C C O C CH3

Ethanoic anhydride

16
Functional Groups
⚫ Acid halide

O
H3 C C Cl
Ethanoyl chloride

17
Functional Groups
⚫ Nitro

O
H3 C N
Nitromethane
O
18
Functional Groups
⚫ Arene

benzene

19
Functional Groups
⚫ Halide

H3 C Cl
Chloromethane

20
Functional Groups
⚫ Nitrile

H3 C C N
Ethanenitrile

21
Functional Groups
⚫ Sulfide

H3 C S CH3

22
Functional Groups
⚫ Thiol

H3 C S H
Methanethiol

23
Functional Groups

O OCH3
O
NH2
N
H

HO O
24
Alkanes and Alkane Isomers
⚫ Alkanes: Compounds with C-C single bonds and C-H
bonds only (no functional groups)
⚫ Connecting carbons can lead to large or small molecules
⚫ The formula for an alkane with no rings in it must be
CnH2n+2 where the number of C’s is n
⚫ Alkanes are saturated with hydrogen (no more can be
added
⚫ They are also called aliphatic compounds

25
Alkanes

H3C CH2 CH2 CH3 CH3CH2CH2CH3 CH3(CH2)2CH3

H H H H H H
H H
H C C C C H C C H
H C C
H H H H H H
H H

CH3CH(CH3)CH2CH3

26
Structure
⚫ Shape
⚫ tetrahedral about carbon
⚫ all bond angles are approximately 109.5°

27
Alkane Isomers
⚫ CH4 = methane, C2H6 = ethane, C3H8= propane
⚫ The molecular formula of an alkane with more than three carbons
can give more than one structure
⚫ C4 (butane) = butane and isobutane

⚫ C5 (pentane) = pentane, 2-methylbutane, and 2,2-

dimethylpropane
⚫ Alkanes with C’s connected to no more than 2 other C’s are
straight-chain or normal alkanes
⚫ Alkanes with one or more C’s connected to 3 or 4 C’s are
branched-chain alkanes

28
Alkanes
⚫ straight chain or normal alkanes

H H H H H H H H H H
H C H H C C H H C C C H H C C C C H
H H H H H H H H H H

29
Alkanes
⚫ branched chains

H
H H C H
H H H H H H C H H H
H C C C C C H H H H H C C C H
H H H H H H C C C C H H H
H H H H H C H
H 30
Branching vs. No Branching
⚫ There are 2 isomeric butanes
H H H H
⚫ n-butane H C C C C H
⚫ C4H10 H H H H
⚫ n means “normal” or in a straight chain

⚫ isobutane
H
⚫ C4H10
H C H
H H
H C C C H
H H H

31
Find the Isomers of C5H12

32
Find the Isomers of C6H14
Draw the structures for C6H14 starting with the longest
chain (6 in a row) H H H H H H

H C C C C C C H

H H H H H H

…next draw all structures with 5 carbons in the longest

chain (substitute for the H s)

…then substitute for other H s

H
H C H
H H H H
H C C C C C H
H H H H H 33
Find the Isomers of C6H14

34
Find the Isomers of C7H16

35
Isomers
⚫ Same chemical
formula, but different
structure.

36
Constitutional Isomers
⚫ Isomers that differ in how their atoms are arranged in chains are
called constitutional isomers
⚫ Compounds other than alkanes can be constitutional isomers
of one another
⚫ They must have the same molecular formula to be isomers

37
Constitutional Isomerism

Mol e cul ar Consti tutional

Form ula Isome rs
CH4 1 World population
C5 H12 3 is about
6,000,000,000
C10 H22 75
C15 H32 4,347
C30 H62 4,111,846,763

38
Names of Small Hydrocarbons
No. of Carbons Formula Name (CnH2n+2)
1 Methane CH4
2 Ethane C2H6
3 Propane C3H8
4 Butane C4H10
5 Pentane C5H12
6 Hexane C6H14
7 Heptane C7H16
8 Octane C8H18
9 Nonane C9H20
10 Decane C10H22
39
Alkyl Groups
⚫ Alkyl group – remove one H from an alkane (a part
of a structure)
⚫ General abbreviation “R” (for Radical, an incomplete
species or the “rest” of the molecule)
⚫ Name: replace -ane ending of alkane with -yl ending
⚫ CH3 is “methyl” (from methane)
⚫ CH2CH3 is “ethyl” from ethane
⚫ See Table 3.4 for a list

40
Types of Alkyl groups
⚫ Classified by the connection site (See Figure 3.3)
⚫ a carbon with one carbon attached to it (primary alkyl group)
⚫ a carbon with two carbons attached to it (secondary alkyl group)

⚫ a carbon with three carbons attached to it (tertiary alkyl group)

⚫ a carbon with four carbons attached to it (quaternary alkyl group)

41
Types of Alkyl groups
⚫ Classified by the connection site (See Figure 3.3)
⚫ a carbon with one carbon attached to it (primary alkyl group)
⚫ a carbon with two carbons attached to it (secondary alkyl group)
⚫ a carbon with three carbons attached to it (tertiary alkyl group)
⚫ a carbon with four carbons attached to it (quaternary alkyl group)

CH3 CH3 CH3

CH3 C CH2CH C CH3
CH3 CH3 42
Degree of Substitution

2
CH3 4 CH 3

CH3CHCHCH2CH2C CH3
1 3
CH2 CH3 CH3
43
Nomenclature

International colloquially:
Union of “eye-you-pac”

Pure and
Applied
Chemistry
Devised following WWII ca. 1946-1950 44
Naming Alkanes
⚫ Compounds are given systematic names by a
process that uses
⚫ Prefix-Parent-Suffix
⚫ Follows specific rules
⚫ Named as longest possible chain
⚫ Carbons in that chain are numbered in sequence
⚫ substituents are numbered at their point of attachment
⚫ Compound name is one word (German style)
⚫ Complex substituents are named as compounds would be

45
Nomenclature
Where are substituents?
Prefix-Parent-Suffix

How many carbons?

What family?
International Union of Pure and Applied Chemistry
(IUPAC) 46
Nomenclature

Prefix-Parent-Suffix
C H 3 C H 2 C H C H 2 C H 2 C H C H 2 C H 3

C H 3 C H 2 C H 3

3-ethyl-6-methyl octane
47
 ◼ Alkanes have the
general formula
Nomenclature CnH2n+2
Name Condensed Structure
Methane CH4
Ethane CH3CH3
Propane CH3CH2CH3
Butane CH3(CH2)2CH3
Pentane CH3(CH2)3CH3
Hexane CH3(CH2)4CH3
Heptane CH3(CH2)5CH3
Octane CH3(CH2)6CH3
Nonane CH3(CH2)7CH3
Decane CH3(CH2)8CH3
Undecane CH3(CH2)9CH3
Dodecane CH3(CH2)10CH3

48
The Longest Continuous Chain
of Carbon Atoms

all possibilites
C-C
must be examined
C-C-C-C-C-C-C-C-C it won’t always be
the horizontal one
C 9 as shown here

try these also ……..

C-C C-C
C- C-C-C -C-C-C-C-C C-C-C- C-C-C-C-C-C
C
C 6 8 49
Nomenclature
⚫ Parent name of the longest carbon chain is
“alkane”
⚫ Groups attached to the parent chain are
called substituents
Each substituent is given a name and a number
⚫ If substituent occurs more than once, di-, tri-,
tetra-, etc.

50
Nomenclature
⚫ Number the chain to give the substituent
encountered first the lowest number
⚫ If there are different substituents, list them in
alphabetical order. The following are not included in
alphabetization.
⚫ di-, tri-, tetra-, etc.
⚫ hyphenated prefixes, such as sec- and tert-

51
Nomenclature

⚫ Alkyl groups
⚫ Propyl -CH2CH2CH3
⚫ Isopropyl -CHCH(CH3)2
⚫ Butyl -CH2CH2CH2CH3
⚫ Isobutyl -CH2CHCH(CH3)2
⚫ sec-butyl -CH(CH3)CH2CH3
⚫ tert-butyl -C(CH3)3

52
Nomenclature

⚫ Alkyl groups

Conde nse d
NamStr
e uc t ur al F o
pe nt yl
-CH
2CH
CH
2 CH
2 CH
2 3

i sope-CH
CHCHCH
ntyl
2 2 3
CH
3
CH
3
-CH
ne ope CCH
ntyl
2 3
53
CH
3
Nomenclature
⚫ Find the longest chain.
CH2 CH3 hexane
CH3CH2CH2CH CH3

CH3
heptane
CH2
H3C CH CH CH2CH3
CH2CH2CH3
54
Nomenclature
⚫ If two different chains of equal length are
present, choose the one with the larger
number of branch points.

CH3
CH3CHCHCH2CH2CH3
CH2 CH3 55
Nomenclature
⚫ Number the atoms in the main chain:
⚫ Begin at the end nearer the first branch point
(lower number).

1 CH3
2 CH2 4
H 3C CH CH CH2 CH3
3
CH2 CH2 CH3
56
5 6 7
Nomenclature
⚫ If branching is equal distant away from both
ends of the parent chain, begin at the end
nearer the second branch point.

H3C CH2 CH3

CH3CHCH2CH2CHCHCH2CH3
CH2 CH3
57
Nomenclature
⚫ Identify the number of substituents:
⚫ Assign a number to each substituent according to
its point of attachment to the main chain.

3-ethyl-4,7-dimethylnonane
9 8 3-ethyl
H3C CH2 CH3 4-methyl
3 7-methyl
CH3CHCH2CH2CHCHCH2CH3
7 6 5 4 CH2 CH3
2 1
58
Nomenclature
⚫ If there are two substituents on the same
carbon, assign them both the same number.

4-ethyl-2,4-dimethylhexane
2-methyl
CH3 CH3 4-methyl
4-ethyl
CH3CH2CCH2CHCH3
CH2 CH3 59
Nomenclature
⚫ Write the name as a single word, using
hyphens to separate the different prefixes
and commas, to separate numbers.
⚫ Use di-, tri-, etc. if more than one identical
substituents
⚫ Don’t use these prefixes for alphabetizing
purposes.

60
Nomenclature

3-methylhexane

CH2 CH3
CH3CH2CH2CH CH3
61
Nomenclature
4-ethyl-3-methylheptane

1 CH
CH33
2 CH
CH224
CH3CHCHCH2CH3
CH33
CHCHCH2CH3
CH2 CH2 CH3
CH2 CH2 CH3
5 6 7 62
Nomenclature

3-ethyl-2-methylhexane

CH3
CH3CHCHCH2CH2CH3
CH2 CH3
63
Nomenclature
⚫ Name a complex substituent and begin
numbering at the point of attachment and set
it off in parentheses.

CH3
CH3CH CHCH2CH2CH CH2CH CH3
CH3 CH3 CH2CH2CH2CH3

64
Nomenclature

2,3-dimethyl-6-(2-methylpropyl)decane

2-methylpropyl
1
CH3
2 3
CH3CH CHCH2CH2CH CH2CH CH3
CH3 CH3 CH2CH2CH2CH3

65
 CH3 CH3
CH CHCH3
Nomenclature

1,2-dimethylpropyl
CH3 CH3
CH3CH2CH2CH2CH CH CHCH3
CH2 CH3
CH2 CH CH3
2-methyl-5-(1,2-dimethylpropyl)nonane

66
Nomenclature-Historical
⚫ Three–carbon alkyl group:

CHCH3

⚫ isopropyl (i-pr)
CH3

67
Nomenclature-Historical
⚫ Four–carbon groups:

CH3
CHCH2CH3 CH2CHCH3
C CH3
CH3 CH3
CH3
sec-butyl isobutyl tert-butyl

68
Nomenclature-Historical
⚫ Five–carbon alkyl groups:

CH3
CH2CH2CHCH3
CH2CCH3
CH3
CH3
isopentyl neopentyl

69
Nomenclature

H3C CH CH3
H3C CH2 CH2 CH CH2 CH2CH3

4-(1-methylethyl)heptane or 4-isopropylheptane

70
If you can name this,
you can name anything!

C H3 C H3

C H3 C H C H2 C H C H2 C C H3
1 2 3 4 5 6
C H3 C H 7 C H2

C H38 9 C H2 C H3

4-isopropyl-2,6,6-trimethylnonane
71
How about this?

CH3

CH3CH2 CH3
CH3

2-cyclobutyl-5-methylhexane 5-ethyl-1,1,3-trimethyl-2-(2-
not methylpentyl)cyclohexane
(1,4-dimethylpentyl)cyclobutane
72
Properties of Alkanes
⚫ Called paraffins (low affinity compounds)
because they do not react as most chemicals
⚫ They will burn in a flame, producing carbon
dioxide, water, and heat
⚫ They react with Cl2 in the presence of light to
replace H’s with Cl’s (not controlled)

73
Physical Properties
⚫ Boiling points and melting points increase as size of
alkane increases
⚫ Forces between molecules (temporary dipoles,
dispersion) are weak

74
Alkane MP & BP Trends
⚫ The dependence of the
boiling and melting
points on chain length
can be explained in
terms of increasing
attractive van der
Waals interactions as
the chain length
increases.

75
Cycloalkanes
⚫ Cycloalkanes are alkanes that have carbon atoms
that form a ring (called alicyclic compounds)
⚫ Simple cycloalkanes rings of ⎯CH2⎯ units, (CH2)n,
or CnH2n
⚫ Structure is shown as a regular polygon with the
number of vertices equal to the number of C’s (a
projection of the actual structure)

cyclobutane
cyclopentane cyclohexane 76
cyclopropane
Cycloalkanes

77
Cycloalkanes
CH2OH
CO
H3C
O OH
H3C

H H
O cortisone
78
Cycloalkanes
⚫ Structure and nomenclature
⚫ to name, prefix the name of the corresponding open-
chain alkane with cyclo-, and name each substituent on
the ring
⚫ if only one substituent, no need to give it a number
⚫ if two or more substituents, number from the substituent
of lowest alphabetical order
⚫ where there is choice, number to give substituents the
lowest set of numbers

79
Naming Cycloalkanes
⚫ Count the number of carbon atoms in the ring and the number in the
largest substituent chain. If the number of carbon atoms in the ring is
equal to or greater than the number in the substituent, the compound is
named as an alkyl-substituted cycloalkane
⚫ For an alkyl- or halo-substituted cycloalkane, start at a point of
attachment as C1 and number the substituents on the ring so that the
second substituent has as low a number as possible.
⚫ Number the substituents and write the name
⚫ if only one substituent, no need to give it a number
⚫ See text for more details and examples

80
Nomenclature
⚫ For alkyl-substituted cycloalkanes, start at the
point of attachment and number the
substituents on the ring so as to arrive at the
lowest sum.

CH3
1 1,3-dimethylcyclohexane
6 2

5 3 not 1,5-dimethylcyclohexane
4
CH3
81
Nomenclature
⚫ Halogens are treated exactly like alkyl
groups.
1-bromo-3-ethyl-5-methylcyclohexane
CH3 Br
3 2

4
1
Br CH3CH2 CH3

1-bromo-2-methylcyclobutane
82
Cis-Trans Isomerism in
Cycloalkanes
⚫ Rotation about C-C bonds in cycloalkanes is limited by the
ring structure
⚫ Rings have two “faces” and substituents are labeled as to
their relative facial positions
⚫ There are two different 1,2-dimethyl-cyclopropane isomers,
one with the two methyls on the same side (cis) of the ring
and one with the methyls on opposite sides (trans)

83
Stereoisomers
⚫ Compounds with atoms connected in the same order but which differ in
three-dimensional orientation, are stereoisomers
⚫ The terms “cis” and “trans” should be used to specify stereoisomeric
ring structures
⚫ Recall that constitutional isomers have atoms connected in different
order

84
Cis-Trans Isomerism

H3 C CH3 H3 C

CH3

cis-1,2-dimethylcyclopropane
trans-1,2- dimethylcyclopropane

85
Cis-trans isomerism
⚫ 1,2-dimethylcyclopentane

H H
H H H H
H H H CH3
H H
H H H H
CH3 CH3 CH3 H
cis-1,2-dimethyl- trans-1,2-dimethyl-
86
cyclopentane cyclopentane
Cis-trans isomerism
⚫ 1,4-Dimethylcyclohexane
⚫ planar hexagon representations

H CH3 H H

H3 C H H3 C CH3
trans-1,4-Dimethyl- cis-1,4-Dimethyl-
cyclohex ane cyclohex ane

87