Chemistry 1102

Charlie Bond
MCS Rm 4.16/4.27
[email protected]

What is Organic Chemistry?

Organic Reactions I II
Alkanes (Ch 21)
Conformational Analysis (Ch 21)
Stereochemistry I II III (Ch 22)
Alkyl Halides I II (Ch 24)
Alcohols and Ether I II (Ch 24)

Problems to do in
Brown&LeMay
21.1- 21.37 except 21.4, 21.15, 21.16
21.19, 21.20
Online self-help study at
www.masteringchemistry.com

Organic Chemistry
Hydrocarbons
Saturated

Class

Alkanes
(Chapter3)

Carbon Onlycarbon
carbon carbonsingle
bonding
bonds
HH
Example
H-C-C-H
HH
Name
Ethane

Unsaturated
Alkenes
(Chapters45)

Alkynes
(Chapter4)

Arenes
(Chapter9)

Oneormore
carboncarbon
doublebonds
H
H
C C
H
H
Ethylene

Oneormore
carboncarbon
triplebonds

Oneormore
benzenelike
rings

ethene

ethyne

H-C C-H
Acetylene

Benzene
3

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 open chain
Aliphatic hydrocarbon: another name for
an alkane
4

Nomenclature
Alkanes have the general formula CnH2n+2
names of unbranched chain alkanes
Molecular
Formula

Name

Molecular
Formula

methane CH4

nonane

C9H2 0

ethane
C2H6
propane C3H8

decane

C10H22

dodecane

C12H26

butane

tetradecane

C14H30

Name

C4H10

pentane C5H12

hexadecane C16H34

hexane

octadecane

C18H38

eicosane

C20H42

C6H14

heptane C7H16
octane
C8H1 8

IUPAC Nomenclature
Common alkyl groups
Name
methyl

Condensed
StructuralFormula
-CH3

ethyl

-CH2CH3

propyl

-CH2CH2CH3

isopropyl -CHCH3
CH3
butyl

-CH2CH2CH2CH3

Name
isobutyl
secbutyl

Condensed
StructuralFormula
-CH2CHCH3
CH3
-CHCH2CH3
CH3

CH3
tertbutyl -CCH3
CH3
6

IUPAC Nomenclature
1.The name of an alkane with an unbranched chain
consists of a prefix and the suffix ane
2. For branched alkanes, the parent chain is the longest
chain of carbon atoms
3. Each substituent is given a name and a number
CH3
2
CH3 CHCH3
1
3
2Methylpropane
4. If there is one substituent, number the chain from the
end that gives it the lower number
CH3

CH3 CH2 CH2CHCH3

2Methylpentane

4 3

1
7

Classification of Carbons

Primary (1): a C bonded to one other carbon

Secondary (2): a C bonded to two other carbons
Tertiary (3): a C bonded to three other carbons
Quaternary (4):
(4) a C bonded to four other carbons

a2carbon

a4carbon
a3carbon
CH3
CH3 -C-CH2-CH-CH3
a1carbon
a1carbon
CH3
CH3
2,2,4Trimethylpentane

Constitutional Isomers
Constitutional isomers: compounds with the same
molecular formula but a different connectivity of their
atoms
there are two constitutional isomers with molecular
formula C4H10

CH3CH2 CH2 CH3

CH3
CH3 CHCH3

Butane
(bp0.5C)

2Methylpropane
(bp11.6C)

Constitutional Isomerism

the potential for constitutional isomerism is

enormous
Molecular
Formula
CH4

Constitutional
Isomers

C5 H12

1
3

C10 H22

75

C15 H32

4,347

C25 H52

36,797,588

C30 H62

4,111,846,763

World population
is
>6,000,000,000

10

Physical Properties
Alkanes are nonpolar compounds and have only
weak interactions between their molecules
Dispersion forces: weak intermolecular forces of
attraction resulting from interaction of temporary
induced dipoles

At Room Temperature:
1-4C are gases (e.g. butane), 5-17C are liquids (e.g.
hexane, kerosene), 18+C are solids/waxes (e.g.
parafin wax).
average density is about 0.7 g/mL
liquid and solid alkanes float on water

11

Physical Properties

Constitutional isomers are different compounds and

have different physical properties
Hexane

Name
hexane
3methylpentane
2methylpentane

Melting Boiling
Point Point Density
(C)
(C) (g/mL)

95
6
23
2,3dimethylbutane 129
2,2dimethylbutane 100

69
64
62
58
50

0.659
0.664
0.653
0.662
0.649

2,2Dimethylbutane

Melting point goes up with branching less flexibility,

molecules can pack together more easily
Boiling point goes down with branching less available
surface area for interactions (e.g. compare spaghetti with 12
spaghetti hoops)

Reactions of Alkanes
Oxidation is the basis for the use of
alkanes as energy sources for heat and
power
heat of combustion: heat released when
one mole of a substance is oxidized to
carbon dioxide and water
CH4 + 2O2
Methane
C2H6 + 3.5O2
CH3 CH2 CH3 + 5O2
Propane

CO2 + 2H2 O

H=212kcal/mol
-886 kJ/mol

2CO2 + 3H2O

Ho = -1427 kJ/mol
H=530kcal/mol
-2215 kJ/mol

3CO2 + 4H2 O

13

Conformations of Ethane
Conformation:
Conformation any three-dimensional arrangement of atoms in a
molecule that results from rotation about a single bond
Staggered Conformation
H

H
H

H
C

H
H

Ethane

60

H
H

Newman projection

Each carbon-hydrogen bond bisects the angle between two

carbon-hydrogen bonds on the other carbon
Each hydrogen on the front carbon is perfectly staggered
between two hydrogens on the back carbon
14

Conformations of Ethane
Eclipsed Conformation
H
H

H
H

H
C

H
H

Ethane

HH

H
H

Newman projection

Each carbon-hydrogen bond on one carbon of the eclipsed

conformation of ethane is directly in line with a carbon-hydrogen
bond on the other carbon
The back carbon-hydrogen bonds lie directly behind the front
carbon-hydrogen bonds
The front hydrogens eclipse the back hydrogens

15

16

Conformations of Butane
H
H

C1
2

H
H

H
Butane

Conformation
analysis about C2-C3
bond of butane is
more complex,
because each carbon
has a methyl group
and two hydrogens
bonded to it

C
H

C
H

H
H

H
C

H
H

H
17

Conformations of Butane
H3C 1
2

H3C 1

CH3

4 CH

H
H

Newman projections
H
H

H
H3C

H
H

CH3
CH3

CH3

CH3
H

H
H3C

staggered conformer

eclipsed conformer

HH

H
H

H3C

eclipsed conformer

CH3
staggered conformer

18

Conformations of Butane
Staggered Conformations
CH3
H

H
H3C
conformer 1

The methyl groups are

said to be anti if the
angle between them is
180
Is the most stable
because is staggered
and has the two methyl
groups as far apart as
possible

H
H

H3C

H
CH3
conformer 2

We can predict that

conformer 1 will be of
lower energy than
alternative staggered
conformer 2
19

Conformations of Butane
Eclipsed Conformations
H3C
CH3
H
H

H
H
conformer 1

The eclipsed
conformation is 19 kJ/
mol higher in energy
than anti, due to a H
with H and CH3 with
CH3 eclipsing
interactions

H
H

H
H3C

CH3

conformer 2

20

 The energy difference between the low-energy

staggered anti conformer and the highest energy
eclipsed conformer is about 19 kJ/mol
21

Physical Properties

Constitutional isomers are different compounds and

have different physical properties
Hexane

Name
hexane
3methylpentane
2methylpentane

Melting Boiling
Point Point Density
(C)
(C) (g/mL)

95
6
23
2,3dimethylbutane 129
2,2dimethylbutane 100

69
64
62
58
50

0.659
0.664
0.653
0.662
0.649

2,2Dimethylbutane

Melting point goes up with branching less flexibility,

molecules can pack together more easily
Boiling point goes down with branching less available
surface area for interactions (e.g. compare spaghetti with 22
spaghetti hoops)

Cycloalkanes
General formula CnH2n
five- and six-membered rings are the most
common
Cyclopentane, cyclohexane

23

Cyclic Molecules in Nature

Steroids are an important class of compounds occurring in all
animals and plants and have many important functions;
hormones, anabolic steroids
O

OH

CH3

H
H
HO

H
H

O
Estradiol

Progesterone

24

Conformations of Cyclohexane
This is a chair conformation
The view along C1 C5 shows that there
are no eclipsing C H
All bonds are fully staggered, giving the
lowest energy possible

This is why cyclohexane is strain free

25

Conformations of Cyclohexane
This is a chair conformation of cyclohexane

Staggered Conformation of Butane

H
H
H

C1
2

H
H

H
Butane

H3C

H
CH3
conformer 2

26

Conformations of Cyclohexane
This is a boat conformation
Now all the C H bonds are eclipsed
Boat conformation is 25 kJ/mol
higher in energy than chair conformation

27

Conformations of Cyclohexane
This is a boat conformation of cyclohexane

Eclipsed Conformation of Butane

H
H

C1
2

H
H

H
Butane

H3C
CH3
H
H

H
H

Newman projection

28

Conformations of Cyclohexane
Staggered conformation
of butane
CH3
H

H
H3C

Newman projection

Eclipsed conformation
of butane
H3C
CH3
H
H

H
H

Newman projection 29

Drawing Cyclohexane
1. Draw two parallel lines, slanted
downward and slightly offset from each
other. This means that four of the
cyclohexane carbon atoms lie in plane.
3. Locate the top most carbon above and
to the right of the plane of the other four
atoms and connect the bonds.
5. Locate the bottom most carbon atom
below and to the left of the plane of the
middle four and connect the bonds.
7. Note that the bonds to the bottom most
carbon are parallel to the bonds to the
top most carbon.

30

Drawing Cyclohexane
1. Start off with one end. Locate
the top carbon on the left.
2. Next draw the two parallel lines
of equal lengths. At this stage,
the top of the new line should
be level with the top of the
original pair.
these lines

Level

should be parallel

6. Finally, the last lines should be

parallel to the first pair of lines
shown, and the lowest points
should also be level.
these lines
31
should be parallel

How Not to Draw Cyclohexane

32

Axial and Equatorial Bonds in Cyclohexane

The chair conformation has two kinds of positions for substituents
on the ring: axial positions and equatorial positions
Chair cyclohexane has six axial hydrogens perpendicular to the
ring (parallel to the ring axis) and six equatorial hydrogens near
the plane of the ring

33

Axial and Equatorial Bonds

34

Conformational Mobility of Cyclohexane

The chair conformations readily interconvert, resulting in the
exchange of axial and equatorial positions by a ring-flip

35

Ring flipping
For an animation, look at
http://www.chem.calgary.ca/courses/351/Carey5th/Ch03/ch3-06.html

36

The Poisonous Pufferfish

FuguFugu is the Japanese word for pufferfish and is also a Japanese
dish prepared from the meat of pufferfish.
"IFugu
want to
fugu, but Iinochi
don't want
die"
waeatkuitashii,
wa to
oshishii
OH
O
HOH2C
OH

O OH

OH
H

NH

HO

N
H

Tetrodotoxin

25 milligrams of tetrodotoxin would be expected to kill a 75 kg person

37

CH3

Conformation of Methylcyclohexane
The two conformers of methylcyclohexane are not equal in
energy
H
H

CH3

H 6H
3

chair
axial 5%

H3C

H
H
boat

H
H

H
H

H5 H
H

H
6

H
1

CH3

chair
equatorial 95%

38

Conformation of Methylcyclohexane
The equatorial conformer of methyl cyclohexane is more stable
than the axial conformer by 7.6 kJ/mol

39

Problem: Which of the following cyclohexanes has the highest

energy?
CH3

CH3

CH3
Cl

Cl

Cl
I

CH3

Cl

II

IV

III

Problem: Which of the following cyclohexanes has the lowest energy?

CH3
H3C C
CH3

CH3

H3C

Cl
CH
3
C

C
CH3
H3C
Cl

Cl
I

CH3

II

III

CH3

C
CH3
H3C

Cl
IV

40

Conformations of Cyclohexane

these H atoms are all

down relative to their partners
on the same C carbon
H

H
H

H
OH

H
H 6H
3

H
H

these H atoms are all

up relative to their partners
on the same C carbon

OH
a
H

e OH
H

41

 What happens with more than one substituent on the cyclohexane

ring? Problem: Draw the conformations of the two isomers of cis and
trans 1,2-cyclohexanediol.
both OH groups occupy positions on the
upper side of the ring

OH
OH

cis - 1,2-cyclohexanediol

OH
OH
trans - 1,2-cyclohexanediol

OH
a 2
H
1 OH
e
H

HO e
2

OH
a
H
1

both H atoms occupy positions on the

lower side of the ring

OH
a 2
H
1 H
a
OH
conformer with both
OH axial

HO e
2

H
1

e
OH

H
the more stable
conformer with both
42
OH equatorial

Problem: Draw the conformations of the two isomers of cis and trans
1,4-cyclohexanediol.
both H atoms occupy positions on the
upper side of the ring

OH

H
OH

trans - 1,4-cyclohexanediol

e
HO

4
1

a
OH

both OH groups occupy positions on the

lower side of the ring

OH

e
OH

a
OH

cis - 1,4-cyclohexanediol

OH

OH
a
H
a
OH
conformer with both
OH axial

H
e
HO

OH

H
the more stable
conformer with both
OH equatorial
43

Draw the preferred conformations of the two isomers

of 1,3,5-trimethylcyclohexane

H3C

axial
equatorial
5

CH3

H3C
CH3

CH3

CH3

H3C

axial
equatorial

CH3

H
CH3

CH3

CH3
H

H3C
44