Power Point to Accompany

Principles and Applications of

Inorganic, Organic, and Biological
Chemistry
Denniston, Topping, and Caret
4th ed

Chapter 11

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

11-1

Organic Chemistry-History
Historically - compounds from living
systems (plants and animals)
A vital force, ie. life was thought to be
necessary to make organic chemicals.
In 1828 Wohler synthesized urea from
purely inorganic chemicals.
Urea, found in urine, was definitely an
organic compound!
O
KCNO + NH4Cl H2N C NH2+ KCl
urea

11-2

Modern Organic Chemistry

The Study of Carbon Compounds
(some exceptions: for example
carbonates, carbon dioxide, etc.)
Biochemistry is now the field that
studies chemicals of life.

11-3

Examples of Organic Chemicals

Foods
Carbohydrates
Fats
Proteins
Clothing
silk, linen, wool,
cotton, Dacron,
Nylon, Orlon,
etc.

Plastics
Pharmaceuticals
Detergents and
Soaps
Pesticides
Gasoline and oils
Water purification

11-4

11.1 Why is Carbon Unique?

1. Forms four covalent bonds
2. Bonds covalently to: H, O, N, P, S, and
all other nonmetals (except noble
gases)
3. Carbon atoms join to form:
H2
a. Chains and b. Rings

CH3CH2CH2CH3

H2C

CH2

H2C CH2

11-5

Why is carbon unique?: 2

4. Carbon can form H2C CH2
multiple bonds to
H2C O
itself, oxygen, and
H2C NH
nitrogen.
double bonds

HC CH
HC N
triple bonds

11-6

Why is Carbon Unique?: 3

4. Many carbon compounds exist in the
form of isomers.
Isomers are compounds with the same
molecular formula but different
structures.
An isomer example: A, B, and C all are
C4H10 but have different structures. See
the next slide!
11-7

Why is Carbon Unique?: 3b

Isomer Examples. All C4H8

CH3CH2CH CH2 A
CH3CH CH CH3 B
CH2 CH2
C
CH2 CH2
11-8

Organic vs Inorganic: Differences

Organic

Inorganic

Bonding

Covalent

Ionic

Physical State
(room temp)

Gas/liquid
common

Solids common

Melting points

Tend to be low

Tend to be very
high

Sol. In water

Tend to be
insoluble

Much higher
percent soluble

Conductivity

Nonconductors

Conduct in soln.
and molten
11-9

Families of Compounds: Hydrocarbons

Hydrocarbons contain only carbon and
hydrogen.
They are nonpolar molecules and
consequently are not soluble in water
but are soluble in typical nonpolar
organic solvents like toluene or
pentane.
Hydrocarbons are constructed of chains
or rings of carbon atoms with sufficient
hydrogens to fulfill carbons need for
four bonds.

11-10

Hydrocarbons

Aliphatics
Aromatics
Structures Based On:
Chains and
nonbenzenoid
rings

Benzene ring

11-11

Hydrocarbons

Aliphatics
Aromatics
Alkanes and cycloalkanes
Alkenes and cycloalkenes
Alkynes and cycloalkynes
11-12

Functional groups
CH3 CH3 ethane
Alkanes are
compounds that
CH3 CH2 CH3
contain only
propanecarbon-carbon and burned in a barbecue grill
carbon-hydrogen
CH2 CH2
single bonds.
CH2

For example:

CH2

CH2 CH2
cyclohexane-a ring alkane
11-13

Functional groups-2
alkenes have a
carbon-carbon
double bond
alkynes have a
carbon-carbon triple
bond

H2C

CH2

ethene: basis of
polyethylene plastics
H
H
CH3

CH2

CH2
CH2

C
CH2

CH2

CH2

CH2

CH2

CH2

CH2

CH2

female silkworm moth

OH sex attractant

HC CH
acetylene-welding gas
in oxyacetylene torch
11-14

Functional groups-3
alcohols have the general
formula:
ROH (R is a carbon
group)
ethers have the general
formulas:
R-O-R, Ar-O-R, Ar-O-Ar
Ar is also a carbon
group but is
aromatic
phenols have the general
formula:
Ar-OH (aromatic only!)

CH3CH2 OH
ethanol,
drinking alcohol

CH3 CH2 O CH2 CH3

diethyl ether, a general

anesthetic

OH
aromatic ring
phenol-an early topical
anesthetic
11-15

Functional groups-4
aldehydes have the O
general formula R1 C H

R1 may be H or
any carbon
group
ketones have the O
general formula R1 C R2

aldehyde carbonyl

O
2H C CH CH2OPO3
OH

glyceraldehyde-3-phosphate
from glucose metabolism
ketone carbonyl

O
O
neither R1 nor R2
CH3C CH2 C O
can be H

acetoacetate ion, product

of fat metabolism
11-16

Functional groups-5
acid groups

O
carboxylic acids have
O
CH2 C OH
the general formula
R1 C OH HO C CO2H condensed
CH2 C OH formula
R1 may be carbon or H
O
citric acid, found in fruits
esters have the general
O
formula
O
ester carbonyl

R1 C O R2

R1 may be carbon or H
but R2 cannot be H or
it would be an acid!

C O CH
3
OH
methyl salicylate
oil of wintergreen
11-17

Functional groups-6
acid chlorides have the
general formula O

R1 C Cl
R1 is usually carbon
anhydrides have the
general formula

O
O
R1 C O C R2

R1 usually is the
same as R2 and
neither is H

O
O
ClC CH2CH2CH2CH2C Cl

pivaloyl chlorideused to make nylon

O O
CH3C O C CH3
acetic anhydrideused to transfer
an acetyl group

11-18

Functional groups-7
amines have one of these
general formulas

R1 NH2

R2
R2
R1 NH R1 N R3

R groups may be alkyl

or aromatic
amides have the general
O
formula
R2
R1 C N
R3
All Rs may be carbon or
H

Tryptophan- an
essential amino O
acid
CH2 CH C OH
N
O

NH2
amine nitrogens

N C CH3

amide bond
acetaminophen-the
HO analgesic found in
Tylenol (Reg)
11-19

Functional Groups-8
thiols (mercaptans) have
the general formula

R1 SH
R1 is any carbon
group
disulfides have the
general formula

R S S R

R is any carbon
group
Rs may be different

COOH
H C CH2 SH
NH2 cysteine, an
amino acid
cystine-anfound
aminoinacid

important in
3-D structure of proteins.

COOH

COOH

H C CH2 S S CH2 C H
NH2

NH2

11-20

Test: Identify the groups 1-9

1 an amine
2 a carboxylic acid
3 an ester
4 an alkene
5 an aldehyde
6 an alcohol
7 a ketone
8 a thiol
9 an anhydride

2.

CH3 CH C

OH

1. NH2

4.

CH2 CH CH CH2
CH3

7. C

CH2

8.

CH2 SH
O
CH3 C

5.

3.
O

CH3

H C
CH
HO CH
CH
HO CH
CH2
OH

CH2

CH3 C

9.

C CH3

OH

6.
OH

11-21

11.2 Alkanes, CnH2n+2

The title shows the general formula for a

chain alkane.
The first ten alkanes are:

methane CH4

hexane C6H12

ethane

heptane C7H16

C 2 H6

propane C3H8

octane

butane

nonane C9H20

C4H10

pentane C5H12

C8H18

decane C10 H22

11-22

Lewis vs Condensed Formulas

The Lewis dot

and condensed
H
H C H CH4
formulas for
H
methane.
The Lewis dot
HH
and condensed H C C H CH3 CH3
HH
formulas for
ethane .
11-23

Drawing Methane and Ethane

H
C

H
in plane

H
behind plane

H in front of plane

H
H

H
109.5 o

Staggered form of ethane

11-24

Lewis vs Condensed Formulas-2

Lewis dot vs condensed formulas: propane.
Terminal carbons condense to CH3 with the
hydrogens usually to the right of the carbon.
Interior carbons condense to CH2 .

H H H
H C C C H CH3CH2CH3
H H H
11-25

Lewis vs Condensed Formulas-3

A branch or substituent on a chain may
be condensed into the chain usually
after the carbon from which it branches.

H
HCH
H
H H H
H C C C C C H
H H Cl H H
CH3CH(CH3)CHClCH2CH3

11-26

IUPAC Names
The IUPAC (International Union of Pure
and Applied Chemistry) is
responsible for chemistry names.
Before learning the IUPAC rules for
naming alkanes, the names and
structures of eight alkyl groups must
be learned.
These alkyl groups are historical names
accepted by the IUPAC and integrated
into modern nomenclature.
11-27

Alkyl Groups

H
H C H
H

H
H C or CH3
H

An alkyl group is an alkane with one

hydrogen atom removed. It is named by
replacing the ane of the alkane name
with -yl.
Methane becomes a methyl group.
11-28

Alkyl Groups-2
All six hydrogens on ethane are
equivalent. Removing one H
generates the ethyl group.

HH
HCCH
HH

CH3 CH2
CH2 CH3
C2H5
11-29

Alkyl Groups-3
Propane: removal of a hydrogen generates
two different propyl groups depending on
whether an end or center H is removed.

CH3 CH2 CH3

CH3CH2CH2
n-propyl

CH3CH CH3
isopropyl

11-30

Alkyl Groups-4a
n-butane gives two butyl groups
depending on whether an end (1o)
or interior (2o) H is removed.

CH3 CH2 CH2 CH3

CH3 CH2 CH2 CH2 CH3 CH CH2 CH3

n-butyl

sec-butyl
11-31

Alkyl Groups-4b
Isobutane gives two butyl groups
depending on whether a 10 or 30 H
is removed.
CH3

CH3 CH CH3

CH3 1 C
CH3 CH CH2
o

isobutyl

CH3
CH3 C CH3
3o C

t-butyl

11-32

IUPAC Names for Alkanes-1

1. The base or parent name for an
alkane is determined by the longest
chain of carbon atoms in the formula.
Note: the longest chain may bend and
twist. It is seldom horizontal!
Any carbon groups not part of the
base chain are called branches or
substituents.
These carbon groups are also called
alkyl groups.

11-33

IUPAC Names for Alkanes-1a

Rules 1 applied. Find the longest chain
in each molecule. (Click for answer.)
A=7
B=8

CH3

A
CH2CH2CH CH2CH3
B CH3
CH2
CH3CH2CH2
CH2
CH3
CH3CH2CH CH2CH CH3
11-34

IUPAC Names for Alkanes-2

2. Number the carbon atoms in the chain
starting from the end with the first
branch. If both branches are equally
from the ends, continue until a point of
difference occurs.

11-35

IUPAC Names for Alkanes-2a

Number the carbon atoms correctly.
Left: first branch is on carbon 3.
Right: first branch is on carbon 3 (From
top) not carbon 4 (If from right).

CH3

CH3

CH2

7 CH3

CH2CH2CH3

5 CH2CH2CH CH2CH3 CH3CH CH2CH

3
2
1
3
4
5
6 CH
2

CH2CH3

this branch would be on C-4

if you started at correct C-8.
11-36

IUPAC Names for Alkanes-3

3. Prefix the branches/substituents
in alphabetical order before the
base/stem name (longest chain).
Halogens usually come first.
Indicate the position of the branch
on the main chain by prefixing its
name with the carbon number to
which it is attached. Separate
numbers and letters with a
hyphen.
11-37

IUPAC Names for Alkanes-3a

CH
3
Name
CH2
CH3
CH3 CH2 CH CH2 CH CH3

4-ethyl-2-methylhexane

11-38

IUPAC Names for Alkanes-3b

Hyphenated and number prefixes are not
considered when alphabetizing groups.
Name the compound below.
5-sec-butyl-4-isopropylnonane

CH3
CH3
CH CH2 CH3
CH CH CH CH2 CH2 CH2 CH3
CH2 CH2 CH3
CH3

11-39

IUPAC Names for Alkanes-4

When a branch/substituent occurs more
than once, prefix the name with di, tri,
tetra,etc. Then prefix the number to
the name with a separate number for
each occurance. Separate numbers
with commas.
eg. 3,4-dimethyl or 4,4,6-triethyl

11-40

IUPAC Names for Alkanes-4a

Name

CH3
CH2CH3
CH3CH CH CH2CH CH2CH3
CH3
5-ethyl-2,3-dimethylheptane
ethyl>dimethyl
11-41

Test: IUPAC Names

Name
CH3 CH3CH CH3
CH2
CH2
CH3C CH2CH2C CH2CH3
CH3
CH2CH2CH2CH3
6-ethyl-6-isobutyl-3,3-dimethyldecane

11-42

Constitutional/Structural Isomers
Constitutional/Structural Isomers differ
in how atoms are connected. The two
isomers of butane are shown below.
The carbon atoms are connected in
different patterns.
CH
3

CH3 CH2 CH2 CH3 CH3 CH CH3

butane
Bp 0.4 oC
Mp 139 oC

Isobutane
Bp 12 oC
Mp 145 oC
11-43

11.3 Cycloalkanes
Cycloalkanes have two less hydrogens than
the corresponding chain alkane.
Hexane=C6H14; cyclohexane=C6H12
To name cycloalkanes, prefix cyclo to the
name of the corresponding alkane.
Place substituents in alphabetical order
before the base name as for alkanes.
For multiple substituents, use the lowest
possible set of numbers. A single
substituent requires no number.
11-44

Cycloalkanes-cont.
H

C
H

or

Cyclopropane

H
C
H
H
C
H
H
C
H

H
C
H
H
C
H H
C
H

or

Cl
C
H
H
C
H
H
C
H
Cl

H
C
CH3
H
C
H H
C
H
CH3

1-chloro-3cyclohexane methylcyclohexane11-45

Cis-trans Isomers in Cycloalkanes

Two groups may be on the same side (cis) of
the imagined plane of the cycloring or they
may be on the opposite side (trans). The
two isomers are referred to geometric or
cis-trans isomers. E. g.
Cl

CH3

Cl

cis-1-chloro-3-ethylcyclohexane
trans-1-chloro-3-ethylcyclohexane

CH3
Cl

Cl Cl

cis-1,4-dichlorolcyclohexane
trans-1,4-dichlorocyclohexane

Cl

11-46

11.4 Conformations of Alkanes

Conformations differ only in rotation about
carbon-carbon single bonds. Two
conformations of butane are shown below.
The first (staggered form) is more stable
because it allows hydrogens to be farther
apart and thus the atoms are less crowded.

Insert Fig 11.6

11-47

Two conformations of Cyclohexane

Chair form
Boat form
(more stable) E=equitorial
A A=axial
H
A
H
H
E A E
E
A
E
E
E
H H
A
A
H

H
H
H

H
H

11-48

11.5 Reactions of Alkanes

All alkanes undergo:
Combustion to carbon dioxide and water
Halogenation to haloalkanes

2 C2H6 + 7 O2

CH3CH3 + Cl2
H

H + Br2

4 CO2 + 6 H2O

heat or
light

heat or
light

CH3CH2Cl +HCl
Br
H
+HBr
11-49

The End
Organic Introduction
Saturated Hydrocarbons
11-50