Alkanes and Cycloalkanes

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

2
Structure
◼ 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 a chain
◼ Aliphatic hydrocarbon: another name for
an alkane

3
Saturated Hydrocarbon Versus
Unsaturated Hydrocarbon
H H
H C C H H C C H
H H H H

4
 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

5
 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
6
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

H
◼ isobutane H C H

C4H10
H H
◼ H C C C H
H H H

7
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°): a carbon bonded to
two other carbons
◼ 2°H: a hydrogen bonded to a 2° carbon

8
Classification of C & H
◼ 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

9
Classification of C & H
◼ primary (1o) - bonded to only 1 other carbon
◼ secondary (2o) - bonded to 2 other carbons
◼ tertiary (3o) - bonded to 3 other carbons
◼ quaternary (4o) - bonded to 4 other carbons

CH3 CH3
CH3 C CH2 CH CH3
CH3 10
Degree of Substitution
C C C
C C
PRIMARY SECONDARY
CONNECTED TO ONE CONNECTED TO TWO
OTHER CARBON OTHER CARBONS

C
C
C C

C
C
C C

TERTIARY QUATERNARY
CONNECTED TO THREE CONNECTED TO FOUR C
OTHER CARBONS OTHER CARBONS
11
 Degree of Substitution

CH 3 2 4 CH 3

CH 3CHCHCH 2CH 2C CH 3
1 3
CH 2 CH 3 CH 3

12
Nomenclature
International colloquially:
Union of “eye-you-pac”

Pure and
Applied
Chemistry
Devised following WWII ca. 1946-1950
13
 ◼ Alkanes have the
general formula
CnH2n+2
Nomenclature
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
14
 Nomenclature
Prefix-Parent-Suffix

How many carbons?

Where are substituents?

What family?
International Union of Pure and Applied
Chemistry (IUPAC)
15
 Nomenclature
Prefix-Parent-Suffix
CH3 CH2 CH CH2 CH2 CH CH2 CH3

CH3 CH2 CH3

octane
3-ethyl-6-methyl

16
 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
17
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.

18
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-

19
Nomenclature
◼ Find the longest chain.
CH2 CH3 hexane
CH3CH2CH2CH CH3

CH 3
heptane
CH 2
H 3C CH CH CH 2CH 3
CH 2CH 2CH 3
20
Nomenclature
◼ If two different chains of equal length
are present, choose the one with the
larger number of branch points.

CH3
CH3CHCHCH2CH2CH3
CH2 CH3
21
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
5 6 7
22
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
23
 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 24
 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
25
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.

26
 Nomenclature
3-methylhexane

CH 2 CH 3
CH 3 CH 2 CH 2 CH CH 3

27
Nomenclature
4-ethyl-3-methylheptane

1 CHCH33
2 CHCH224
CH 3
CH33 CHCHCH 2
CHCHCH2CHCH 3
3
CH2 CH2 CH3
CH2 CH 2 CH3
5 6 7
28
Nomenclature
3-ethyl-2-methylhexane

CH3
CH3CHCHCH2CH2CH3
CH2 CH3
29
 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

30
 Nomenclature
2,3-dimethyl-6-(2-methylpropyl)decane

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

31
 Nomenclature

CH 3 CH 3
CH 3CH 2CH 2CH 2CH CH CHCH 3
CH 2 CH 3
CH 2 CH CH 3
2-methyl-5-(1,2-dimethylpropyl)nonane

32
Nomenclature-Historical
◼ Three–carbon alkyl group:

CHCH3
CH3
◼ isopropyl (i-pr)

33
Nomenclature-Historical
◼ Four–carbon groups:
CH3
CHCH2CH3 CH2CHCH3
C CH3
CH3 CH3
CH3
sec-butyl isobutyl tert-butyl

34
Nomenclature-Historical
◼ Five–carbon alkyl groups:
CH3
CH2CH2CHCH3
CH2CCH3
CH3
CH3
isopentyl neopentyl

35
 Nomenclature
H3C CH CH3
H3C CH2 CH2 CH CH2 CH2CH3

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

36
 If you can name this,
you can name anything!
CH3 CH3

CH3 CH CH2 CH CH2 C CH3

1 2 3 4 5 6
CH3 CH CH2
7
CH3 CH2 CH3
8 9
2,6,6- trimethyl- 4(1-methylethyl) nonane
4-isopropyl-2,6,6-trimethylnonane 37
Here are some examples:

40
41
Isomers
◼ Same chemical
formula, but
different structure.

48
Constitutional Isomerism
◼ Compounds isomers: compounds with
the same molecular formula but a
different connectivity (order of
attachment of their atoms)
◼ example: C4H10

CH 3
CH 3 CH 2 CH 2 CH 3 CH 3 CHCH 3
Butane 2-Methylpropane 49
Isomers
◼ Constitutional
H
isomers have H C H

atoms connected H H H H
H C C C C H
H
H C C C H
H

differently H H H H H H H

50
Constitutional Isomerism
Molecular Constitutional
Formula Isomers
CH 4 1 World population
C 5 H 12 3 is about
6,000,000,000
C 10 H 22 75
C 15 H 32 4,347
C 30 H 62 4,111,846,763

52
Find the Isomers of C6H14

54
Find the Isomers of C5H12

55
Find the Isomers of C7H16

56
Cycloalkanes

57
 Cycloalkanes

• Hydrocarbons where the carbons form a ring or cyclic

structure; General formula: CnH2n.

8–59

John A. Schreifels Chapter 24-59

Chemistry 212
8–60
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

61
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
◼ See text for more details and examples
 Nomenclature
◼ Count the number of substituents on
the ring and the number in the largest
substituent. Name according to the
largest substituent.

CH3 CH2 CH2 CH2 CH3

methylcyclopentane 1-cyclopropylbutane
63
 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.
CH 3
1 1,3-dimethylcyclohexane
6 2

5 3 not 1,5-dimethylcyclohexane
4
CH 3

64
 Nomenclature
◼ Halogens are treated exactly like alkyl
groups.
1-bromo-3-ethyl-5-methylcyclohexane

1-bromo-2-methylcyclobutane
68
 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
Name and number the substituents. No number is
needed to indicate the location of a single substituent.

77
With two different substituents, assign numbers to the
substituents alphabetical order.

78
Two contrasting examples: Naming compounds containing
both a ring and a long chain of carbon atoms

79
80
Cis-Trans Isomerism
◼ C-C bonds have free rotation
◼ Rotation is restricted in cyclic
structures.
◼ Cyclic structures have a top and a
bottom.
H3 C CH 3 H3 C

CH 3
81
Cis-Trans Isomerism
◼ Stereoisomers have their atoms
connected in the same order but differ
in three-dimensional orientation.
◼ cis–substituents are on the same side
◼ trans–substituents are on opposite sides

82
 Cis-Trans Isomerism
H3 C CH3 H3 C

CH3

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

83