Organic Chemistry

HIDROCARBON OF ALKANES,
ALKENES AND ALKYNES

Alkane Formulas
H H H H
All

C-C single
bonds
Saturated with
hydrogens
Ratio: CnH2n+2
Alkane homologs:
CH3(CH2)nCH3
Same ratio for
branched alkanes

H C

C C

H H H H
Butane, C 4H10

H
H C

H
H
H C C C H
H H H
Isobutane, C 4H10

Chapter 3

Common Names
Isobutane,

isomer of

butane
Isopentane, isohexane, etc.,
methyl branch on next-to-last
carbon in chain.
Neopentane, most highly
branched
Five possible isomers of
hexane,
18 isomers of octane and 75
Chapter 3

Pentanes
H
H C

H H H H H
H C C C

C C H

H H H H H
n-pentane, C 5H12

CH3
H3C

H H
H
H C C C C H
H H H H
isopentane, C 5H12

C CH3
CH3

neopentane, C 5H12
Chapter 3

=>
4

IUPAC Names
Find

the longest continuous carbon

chain.
Number the carbons, starting
closest to the first branch.
Name the groups attached to the
chain, using the carbon number as
the locator.
Alphabetize substituents.
Use di-, tri-, etc., for multiples of
Chapter 3

Longest Chain
The

number of carbons in the

longest chain determines the base
name: ethane, hexane. (Listed in
Table 3.2, page 81.)
If there are two possible chains
with the same number of carbons,
use the chain withH3Cthe most
CH CH2 CH3
substituents.
CH3

H3C CH2

CH

CH2

CH3

CH2

CH3

=>
Chapter 3

Number the Carbons

Start

at the end closest to the first

attached group.
If two substituents are equidistant,
look for the next closest group.
1

H3C

CH3

CH CH CH2
2

CH2CH3

CH3

CH2

CH CH3
6

7
=>

Chapter 3

Name Alkyl Groups

CH3-,

methyl

CH3CH2-,

CH3

ethyl

CH3CH2CH2-,

n-propyl

CH3CH2CH2CH2-,
CH3 CH

CH3

isopropyl

CH3

CH3

isobutyl

n-butyl

CH CH2

CH CH2

CH3

sec-butyl

CH3
H3C

CH3
tert-butyl

=>
Chapter 3

Propyl Groups
H H H
H C

C C

H H H
H

H C

C C

H H H

H H H

n-propyl

isopropyl

A primary carbon

A secondary carbon
=>

Chapter 3

Butyl Groups
H H H H
H C

C C

H H H H
n-butyl
A primary carbon

H H H H
H

H C
H

C C

H H H
sec-butyl

A secondary carbon
=>
Chapter 3

10

Isobutyl Groups
H

C H
H
H

C H
H
H
H C

H C

C H

H H H

H H H

isobutyl

tert-butyl

A primary carbon

A tertiary carbon
=>
Chapter 3

11

Alphabetize
Alphabetize

substituents by name.
Ignore di-, tri-, etc. for
alphabetizing.
CH3

H3C

CH3

CH CH CH2

CH2

CH CH3

CH2CH3
3-ethyl-2,6-dimethylheptane
=>
Chapter 3

12

Complex
Substituents

If

the branch has a branch,

number the carbons from the point
of attachment.
Name the branch off the branch
using a locator number.
Parentheses are used around the
complex branch name.
1
2

3
1-methyl-3-(1,2-dimethylpropyl)cyclohexane
Chapter 3

13

Physical Properties
Solubility:

hydrophobic
Density: less than 1 g/mL
Boiling points increase with
increasing carbons (little less for
branched chains).
Melting points increase with
increasing carbons (less for oddnumber of carbons).

Chapter 3

14

Boiling Points of
Alkanes
Branched alkanes have less surface area contact,
so weaker intermolecular forces.

=>

Chapter 3

15

Melting Points of
Alkanes

Branched alkanes pack more efficiently into

a crystalline structure, so have higher m.p.

=>

Chapter 3

16

Branched Alkanes
Lower

b.p. with increased

branching
Higher m.p. with increased
branching
Examples:
CH3
CH
3

CH3

CH CH2 CH2 CH3

bp 60C
mp -154C

CH3

CH3

CH

CH

CH3
CH3

bp 58C
mp -135C

CH3
C CH2 CH3
CH3

bp 50C
mp -98C

=>
Chapter 3

17

Major Uses of Alkanes

C1-C2:

gases (natural gas)

C3-C4:

liquified petroleum (LPG)

C5-C8:

gasoline

C9-C16:

diesel, kerosene, jet fuel

C17-up:

lubricating oils, heating oil

Origin:

petroleum refining

=>
Chapter 3

18

Reactions of Alkanes
Combustion
2 CH3CH2CH2CH3

heat

+ 13 O2

8 CO2

+ 10 H2O

Cracking and hydrocracking (industrial)

long-chain alkanes

catalyst

shorter-chain alkanes

Halogenation
CH4 + Cl2

heat or light

CH3Cl + CH2Cl2 + CHCl3 + CCl4

=>
Chapter 3

19

Conformers of Alkanes
Structures

resulting from the free

rotation of a C-C single bond
May differ in energy. The lowestenergy conformer is most
prevalent.
Molecules constantly rotate
through all the possible
conformations.
=>
Chapter 3

20

Ethane Conformers
Staggered

conformer has lowest

energy.
Dihedral angle = 60 degrees
H

model

=>

H
Newman
projection

sawhorse
Chapter 3

21

Cycloalkanes
Rings

of carbon atoms (CH2

groups)
Formula: CnH2n
Nonpolar,

insoluble in water
Compact shape
Melting and boiling points similar
to branched alkanes with same
number of carbons
=>

Chapter 3

22

Naming Cycloalkanes
Cycloalkane

usually base compound

Number carbons in ring if >1
substituent.
First in alphabet gets lowest
number.
2CH3
May beCHcycloalkyl
attachment to
chain. CH2CH3
CH3

=>

Chapter 3

23

Cis-Trans Isomerism

Cis:

like groups on same side of ring

Trans: like groups on opposite sides
of ring
=>
Chapter 3

24

Cycloalkane Stability
5-

and 6-membered rings most

stable
Bond angle closest to 109.5
Angle (Baeyer) strain
Measured by heats of combustion
per -CH2 =>
Chapter 3

25

Heats of Combustion Alkane

+ O2 CO2 + H2O
166.6 164.0
157.4

158.7

158.6
158.3
157.4

=>

Long-chain
Chapter 3

26

Cyclopropane
Large

ring strain due to angle

compression
Very reactive, weak bonds

=>
Chapter 3

27

Cyclopropane (2)
Torsional strain because of eclipsed
hydrogens

=>
Chapter 3

28

Cyclobutane
Angle

strain due to compression

Torsional strain partially relieved
by ring-puckering

=>
Chapter 3

29

Cyclopentane
planar, angles would be 108, but all
hydrogens would be eclipsed.
Puckered conformer reduces torsional
strain.
If

=>
Chapter 3

30

Cyclohexane
Combustion

data shows its

unstrained.
Angles would be 120, if planar.
The chair conformer has 109.5
bond angles and all hydrogens are
staggered.
No angle strain and no torsional
strain.
Chapter 3

31

Chair Conformer

=>

Chapter 3

32

1,3-Diaxial Interactions

=>
Chapter 3

33

Disubstituted
Cyclohexanes

=>
Chapter 3

34

Cis-Trans Isomers
Bonds that are cis, alternate axialequatorial around the ring.
CH3
CH3
=>
Chapter 3

35

Bulky Groups
Groups

like t-butyl cause a large

energy difference between the axial
and equatorial conformer.
Most stable conformer puts t-butyl
equatorial regardless of other
substituents.

Chapter 3

=>
36

Bicyclic Alkanes
Fused

rings share two adjacent carbons.

Bridged rings share two nonadjacent
Cs.

bicyclo[3.1.0]hexane

bicyclo[2.2.1]heptane

bicyclo[3.1.0]hexane

bicyclo[2.2.1]heptane
=>
Chapter 3

37

Cis- and Trans-Decalin

Fused

cyclohexane chair conformers

Bridgehead Hs cis, structure more
flexible
Bridgehead Hs trans, no ring flip
possible.
H
H
=>

cis-decalin

trans-decalin
Chapter 3

38

End of Chapter 3

Chapter 3

39