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Organic Chemistry I:

Formulas, Names,
and Properties
2
Chapter Goals
Saturated Hydrocarbons
1. Alkanes and Cycloalkanes
2. Naming Saturated Hydrocarbons
Unsaturated Hydrocarbons
3. Alkenes
4. Alkynes
Aromatic Hydrocarbons
5. Benzene
6. Other Aromatic Hydrocarbons
7. Hydrocarbons: A Summary
3
Chapter Goals
Functional Groups
8. Organic Halides
9. Alcohols and Phenols
10.Ethers
11.Aldehydes and Ketones
12.Amines
13.Carboxylic Acids
14.Some Derivatives of Carboxylic Acids
15.Summary of Functional Groups
4
Chapter Goals
Fundamental Classes of
Organic Reactions
16.Substitution Reactions
17.Addition Reactions
18.Elimination Reactions
19.Polymerization Reactions
5
Saturated Hydrocarbons
Hydrocarbons are chemical compounds
that contain only C and H atoms.
Saturated hydrocarbons contain only
single or sigma (o) bonds.
There are no double or triple bonds in these
compounds.
The primary source of hydrocarbons is
petroleum and natural gas.
6
Alkanes and Cycloalkanes
The simplest saturated hydrocarbons are
called alkanes.
Methane, CH
4
, is the simplest alkane.
The alkanes form a homologous series.
Each member of the series differs by a
specific number and kind of atoms.
C
H
H
H
H
or CH
4
7
Alkanes and Cycloalkanes
The alkanes differ from each other by a CH
2
or
methylene group.
All alkanes have this general formula.
C
n
H
2n+2
For example ethane, C
2
H
6
, and propane, C
3
H
8

, are the next two family members.
8
Alkanes and Cycloalkanes
Isomers are chemical compounds that
have the same molecular formulas but
different structures.
Two alkanes have the molecular formula
C
4
H
10
.
They are a specific type of isomer called
structural isomers.
9
Alkanes and Cycloalkanes
Three alkanes have the formula C
5
H
12
.

There are three structural isomers of pentane.
C H
3
C
H
2
C
H
2
C
H
2
CH
3
n-pentane
10
Alkanes and Cycloalkanes
Three alkanes have the formula C
5
H
12
.

There are three structural isomers of pentane.
C H
3
C
H
2
C
H
2
C
H
2
CH
3
C H
3
C
H C
H
2
CH
3
CH
3
n-pentane 2-methylbutane
11
Alkanes and Cycloalkanes
Three alkanes have the formula C
5
H
12
.

There are three structural isomers of pentane.
12
Alkanes and Cycloalkanes
There are five isomeric hexanes, C
6
H
14
.
You draw them!
C H
3
C
H
2
C
H
2
C
H
2
C
H
2
CH
3
n-hexane
13
Alkanes and Cycloalkanes
There are five isomeric hexanes, C
6
H
14
.
C H
3
C
H
2
C
H
2
C
H
2
C
H
2
CH
3
C H
3
C
H C
H
2
C
H
2
CH
3
CH
3
n-hexane 2-methylpentane
14
Alkanes and Cycloalkanes
There are five isomeric hexanes, C
6
H
14
.
C H
3
C
H
2
C
H
2
C
H
2
C
H
2
CH
3
C H
3
C
H C
H
2
C
H
2
CH
3
CH
3
C H
3
C
H
2
C
H C
H
2
CH
3
CH
3
n-hexane 2-methylpentane 3-methylpentane
15
Alkanes and Cycloalkanes
There are five isomeric hexanes, C
6
H
14
.
C H
3
C
H
2
C
H
2
C
H
2
C
H
2
CH
3
C H
3
C
H C
H
2
C
H
2
CH
3
CH
3
C H
3
C
H
2
C
H C
H
2
CH
3
CH
3
C H
3
C
C
H
2 CH
3
CH
3
CH
3
n-hexane 2-methylpentane 3-methylpentane
2,2-dimethylbutane
16
Alkanes and Cycloalkanes
There are five isomeric hexanes, C
6
H
14
.
C H
3
C
H
2
C
H
2
C
H
2
C
H
2
CH
3
C H
3
C
H C
H
2
C
H
2
CH
3
CH
3
C H
3
C
H
2
C
H C
H
2
CH
3
CH
3
C H
3
C
C
H
2 CH
3
CH
3
CH
3
C H
3
C
H C
H CH
3
CH
3
CH
3
n-hexane 2-methylpentane 3-methylpentane
2,2-dimethylbutane 2,3-dimethylbutane
17
Alkanes and Cycloalkanes
The number of structural isomers increases
rapidly with increasing numbers of carbon
atoms.
The boiling points of the alkanes increase with
molecular weight.
18
Alkanes and Cycloalkanes
Cyclic saturated hydrocarbons are called
cycloalkanes.
They have the general formula C
n
H
2n
.
Some examples are:
C
H
2
C
H
2
CH
2
C
H
2
C H
2
cyclopentane
19
Alkanes and Cycloalkanes
Cyclic saturated hydrocarbons are called
cycloalkanes.
They have the general formula C
n
H
2n
.
Some examples are:
C
H
2
C
H
2
CH
2
C
H
2
C H
2
C H
2
C H
2
C
H
2
CH
2
CH
2
C
H
2
cyclopentane cyclohexane
20
Alkanes and Cycloalkanes
Cyclic saturated hydrocarbons are called
cycloalkanes.
They have the general formula C
n
H
2n
.
Some examples are:
21
Naming Saturated Hydrocarbons
The International Union of Pure and Applied Chemistry
(IUPAC) names for the first 12 "straight-chain" or "normal"
alkanes are given in this table.

Number of carbon
atoms in chain Name
1 Methane
2 Ethane
3 Propane
4 Butane
5 Pentane
6 Hexane
22
Number of carbon
atoms in chain Name
7 Heptane
8 Octane
9 Nonane
10 Decane
11 Unidecane
12 Dodecane
Naming Saturated Hydrocarbons
23
Naming Saturated Hydrocarbons
Other organic compounds are named as
derivatives of the alkanes.
Branched-chain alkanes are named by the
following rules.
1. Choose the longest continuous chain of
carbon atoms which gives the basic name or
stem.
24
Naming Saturated Hydrocarbons
2 Number each carbon atom in the basic chain, starting at
the end that gives the lowest number to the first group
attached to the main chain (substituent).
3 For each substituent on the chain, we indicate the
position in the chain (by an Arabic numeric prefix)
and the kind of substituent (by its name).
The position of a substituent on the chain is indicated by the
lowest number possible.
The number precedes the name of the
substituent.
25
Naming Saturated Hydrocarbons
4 When there are two or more substituents of a given kind,
use prefixes to indicate the number of substituents.
di = 2, tri = 3, tetra = 4, penta = 5, hexa = 6, hepta = 7, octa =
8, and so on.
5 The combined substituent numbers and names serve as a
prefix for the basic hydrocarbon name.
6 Separate numbers from numbers by commas and
numbers from words by hyphens.
Words are "run together".
26
Naming Saturated Hydrocarbons
Alkyl groups (represented by the symbol R) are
common substituents.
Alkyl groups are fragments of alkanes in which one
H atom has been removed for the connection to the
main chain.
Alkyl groups have the general formula C
n
H
2n+1
.
In alkyl groups the -ane suffix in the name of the parent
alkane is replaced by -yl.
A one carbon group is named methyl.
A two carbon group is named ethyl.
A three carbon group is named propyl.
27
Unsaturated Hydrocarbons
The three classes of unsaturated
hydrocarbons are:
1. alkenes and cycloalkenes, C
n
H
2n

2. alkynes and cycloalkynes, C
n
H
2n-2

3. aromatic hydrocarbons
28
Alkenes
The simplest alkenes contain one C=C bond per
molecule.
The general formula for simple alkenes is C
n
H
2n
.
The first two alkenes are:
ethene, C
2
H
4

29
Alkenes
The simplest alkenes contain one C=C bond per
molecule.
The general formula for simple alkenes is C
n
H
2n
.
The first two alkenes are:
and propene, C
3
H
6
30
Alkenes
Each doubly bonded C atom is sp
2
hybridized.
The sp
2
hybrid consists of:
two o bonds (single bonds) and
one o and one t bond (double bond)
31
Alkenes
The systematic naming system for alkenes uses the
same stems as alkanes.
In the IUPAC system, the -ane suffix for alkanes is
changed to -ene.
Common names for the alkenes have the same stem but use
the suffix -ylene is used.
In chains of four or more C atoms, a numerical prefix
shows the position of the lowest-numbered doubly
bonded C atom.
Always choose the longest chain that contains the C=C
bond.
32
Alkenes
Polyenes contain two or more double bonds per
molecule.
Indicate the number of double bonds with suffixes:
-adiene for two double bonds.
-atriene for three double bonds, etc.
The positions of the substituents are indicated as for
alkanes.
The position of the C=C bond(s) is/are given the
lowest number(s) possible.
33
Alkenes
C
C
C
C
C
C
H
H H
H
H
H
H
H
H
H
1,3-hexadiene
34
Alkenes
C
C
C
C
C
C H
H H
H
H
H
H
H
1,3,5-hexatriene
C
C
C
C
C
C H
H H
C
C
H
H
H
H
H H
H
H H
2,3-dimethyl-1,3,5-hexatriene
C
C
C
C
C
C
H
H H
H
H
H
H
H
H
H
1,3-hexadiene
35
Cycloalkenes
Cycloalkenes have the general formula C
n
H
2n-2
.
Examples are:
cyclopentene
C C
C
C
C
H
H
H
H H
H
H
H
36
Cycloalkenes
cyclohexene
C
C
C
C
C
C H
H
H
H
H
H
H
H
H
H
37
Cycloalkenes
cycloheptene
C
C
C
C
C
C
C
H
H
H
H
H
H
H
H
H
H
H
H
38
Alkynes
Alkynes contain CC bonds.
The simplest alkyne is C
2
H
2
, ethyne, or acetylene.
Alkynes with only one C C bond have the formula
C
n
H
2n-2
.

Each carbon atom in a C C bond is sp hybridized.
Each sp hybrid contains two o bonds and two t bonds.
The carbon atom will have one single bond and one
triple bond.
39
Alkynes
Alkynes are named like the alkenes except
that the suffix -yne is used with the
characteristic stem
The alkyne stem is derived from the name of the
alkane with the same number of carbon atoms.
40
Alkynes
Acetylene is an important industrial chemical.
It is prepared by the reaction of calcium carbide
with water.
( ) ( ) ( ) ( ) s g 2 2 2 s 2
CaO H C O H CaC + +

41
Alkynes
Acetylene burns in a highly exothermic reaction
The combustion produces temperatures of about 3000C.
Acetylene is used in cutting torches for welding.
Alkynes are very reactive
The two t bonds are sights of special reactivity.
Addition reactions, such as hydrogenation, are common.
( ) ( ) ( ) ( ) g 2 g 2 g 2 g 2 2
O H 2 CO 4 5O H 2C + +
( ) ( ) ( ) g 6 2 g 2 g 2 2
H C 2H H C +
42
Hydrocarbons: A Summary
Carbon Atom
Hybridization C uses C forms Example
sp
3
tetrahedral
4 sp
3
hybrids
4 o
bonds
CH
4
sp
2
trigonal planar
3 sp
2
hybrids
& 1p orbital
3 o
bonds
1 t bond
C
2
H
4
sp linear
2 sp hybrids &
2 p orbitals
2 o
bonds
2 t
bonds
C
2
H
2
43
Aromatic Hydrocarbons
Historically, aromatic was used to describe
pleasant smelling substances.
Now it refers to benzene, C
6
H
6
,

and derivatives
of benzene.
Other compounds that have similar chemical
properties to benzene are also called aromatic.
44
Benzene
The structure of benzene, C
6
H
6
, is:
45
Other Aromatic Hydrocarbons
Coal tar is the common source of benzene and
many other aromatic compounds.
Some aromatic hydrocarbons that contain
fused rings are:
napthalene
46
Other Aromatic Hydrocarbons
phenanthrene


C
C
C
C
C
C
C
C
C
C
C
C
C
C
H
H
H
H
H
H
H
H
H
H
47
Other Aromatic Hydrocarbons
Many aromatic hydrocarbons contain alkyl
groups attached to benzene rings (as well as to
other aromatic rings).
The positions of the substituents on benzene
rings are indicated by the prefixes:
ortho- (o-) for substituents on adjacent C atoms
meta- (m-) for substituents on C atoms 1 and 3
para- (p-) for substituents on C atoms 1 and 4
48
Functional Groups
Functional groups are groups of atoms that
represent potential reaction sites.
Compounds that contain a given functional
group usually undergo similar reactions.
Functional groups influence physical
properties as well.

49
Organic Halides
A halogen atom may replace almost any hydrogen
atom in a hydrocarbon.
The functional group is the halide (-X) group.
Examples include:
chloroform, CHCl
3
C
Cl Cl
Cl
H
50
Organic Halides
1,2-dichloroethane, ClCH
2
CH
2
Cl
C C H
Cl
H
H
Cl
H
H
C
H H
H
51
Organic Halides
para-dichlorobenzene
Cl
Cl
52
Alcohols and Phenols
The functional group in alcohols and phenols is
the hydroxyl (-OH) group.
Alcohols and phenols can be considered
derivatives of hydrocarbons in which one or
more H atoms have been replaced by -OH
groups.
Phenols are derivatives of benzene in which one
H has been replaced by replaced by -OH group.
53
Alcohols and Phenols
Ethyl alcohol (ethanol), C
2
H
5
OH, is the most
familiar alcohol.
54
Alcohols and Phenols
Phenol, C
6
H
5
OH, is the most familiar phenol.
OH
55
Alcohols and Phenols
Alcohols are considered neutral compounds
because they are only very slightly acidic.
Alcohols can behave as acids but only in the presence
of very strong bases.
Phenols are weakly acidic.
K
a
~ 1.0 x 10
-10
for phenol
Although phenols are very weakly acidic, they
are also very corrosive.

56
Alcohols and Phenols
Alcohols can be classified into three classes:
1. Primary (1) alcohols like ethanol have the -
OH group attached to a C atom that has one
bond to another C atom.
C H
3
C
H
2
OH
57
Alcohols and Phenols
2. Secondary(2) alcohols have the OH group
attached to a C atom that has bonds to 2 other
C atoms.
For example,2-propanol:
C H
3
C H
C H
3
OH
58
Alcohols and Phenols
3. Tertiary (3) alcohols have the OH group
attached to a C atom that is bonded to 3 other
C atoms.
For example, 2-methyl-2-propanol

C H
3
C CH
3
OH
CH
3
59
Alcohols and Phenols
The stem for the parent hydrocarbon plus an -ol
suffix is the systematic name for an alcohol.
A numeric prefix indicates the position of the -OH
group in alcohols with three or more C atoms.
Common names are the name of the appropriate
alkyl group plus alcohol.

60
Alcohols and Phenols
Alcohols are named using the stem for the parent
hydrocarbon plus an -ol suffix in the systematic
nomenclature.
A numeric prefix indicates the position of the -OH group
in alcohols with three or more C atoms.
Common alcohol names are the name of the appropriate
alkyl group plus the word alcohol.
C H
2
C
H
2
C
H
2
C
H
2
CH
3
OH
C H
3
C
H C
H
2
C
H
2
CH
3
OH
1-pentanol
1-pentyl alcohol
2-pentanol
2-pentyl alcohol
C H
2
C
H
2
C
H
2
C
H
2
CH
3
OH
1-pentanol
1-pentyl alcohol
C H
2
C
H
2
C
H
2
C
H
2
CH
3
OH
C H
3
C
H C
H
2
C
H
2
CH
3
OH
C H
3
C
H
2
C
H C
H
2
CH
3
OH
1-pentanol
1-pentyl alcohol
2-pentanol
2-pentyl alcohol
3-pentanol
3-pentyl alcohol
61
Alcohols and Phenols
There are several isomeric monohydric acyclic
(contains no rings) alcohols that contain more
than three C atoms.
There are four isomeric four-carbon alcohols.
62
Alcohols and Phenols
There are eight isomeric five-carbon alcohols.
You do it!
C
H
2
C
H
2
C
H
2
C
H
2
CH
3
O H
C H
3
C
H C
H
2
C
H
2
CH
3
OH
C H
3
C
H
2
C
H C
H
2
CH
3
OH
1-pentanol 2-pentanol 3-pentanol
C
H
2
C
H
C
H
2
CH
3
O H
CH
3
C H
3
C CH
2
CH
3
CH
3
OH
C H
3
C
H C
H CH
3
OH
CH
3
2-methyl-1-butanol 2-methyl-2-butanol 3-methyl-2-butanol
C H
3
C
H C
H
2
C
H
2
CH
3
OH
3-methyl-1-butanol
C H
3
C C
H
2
CH
3
CH
3
OH
2,2-dimethyl-1-propanol
63
Alcohols and Phenols
Polyhydric alcohols contain more than one -OH
group per molecule.
C H
2
C
H CH
2
OH
OH
OH
C
H
2
C
H C
H C
H C
H CH
2
O H
OH
OH
OH
OH
OH
glycerin sorbitol
64
Alcohols and Phenols
Phenols are usually called by their common
(trivial) names.
OH
OH
resorcinol
65
Alcohols and Phenols
Phenols are usually called by their common
(trivial) names.
OH
OH
OH
CH
3
resorcinol o-cresol
66
Alcohols and Phenols
Phenols are usually called by their common
(trivial) names.
OH
OH
OH
CH
3
OH
CH
3
resorcinol o-cresol m-cresol
67
Alcohols and Phenols
Phenols are usually called by their common
(trivial) names.
OH
OH
OH
CH
3
OH
CH
3
OH
CH
3
resorcinol o-cresol m-cresol p-cresol
68
Alcohols and Phenols
Because the -OH group is quite polar, the properties of
alcohols depend upon the number of -OH groups per
molecule and the size of the organic group.
The boiling points of monohydric alcohols increase with
increasing molecular weight.
The solubility of monohydric alcohols in water decrease
with increasing molecular weight.
Polyhydric alcohols are more soluble in water because of
the two or more polar groups (-OH).
69
Ethers
Ethers may be thought of as derivatives of water
in which both H atoms have been replaced by
alkyl or aryl groups.
H
O
H
water
70
Ethers
Ethers may be thought of as derivatives of water
in which both H atoms have been replaced by
alkyl or aryl groups.
H
O
H
C H
3
O
H
water an alcohol
71
Ethers
Ethers may be thought of as derivatives of water
in which both H atoms have been replaced by
alkyl or aryl groups.
H
O
H
C H
3
O
H C H
3
O
CH
3
water an alcohol an ether
72
Ethers
Ethers are not very polar and not very reactive.
They are excellent solvents.
Common names are used for most ethers.

73
Aldehydes and Ketones
The functional group in aldehydes and ketones is
the carbonyl group.
O
R2 R1 or H
carbonyl group
74
Aldehydes and Ketones
Except for formaldehyde, aldehydes have one H
atom and one organic group bonded to a carbonyl
group.
75
Aldehydes and Ketones
Ketones have two organic groups bonded to a
carbonyl group.
76
Aldehydes and Ketones
Common names for aldehydes are derived from
the name of the acid with the same number of C
atoms.
IUPAC names are derived from the parent
hydrocarbon name by replacing -e with -al.
C
O
C
H
2
C
H
2
C
H
2
C H
3
H
pentanal
or
pentyl aldehyde
77
Aldehydes and Ketones
Common names for aldehydes are derived from
the name of the acid with the same number of C
atoms.
IUPAC names are derived from the parent
hydrocarbon name by replacing -e with -al.
C
O
C
H
2
C
H
2
C
H
2
C H
3
H
C
O
C
C H
3
C H
3
CH
3
H
pentanal
or
pentyl aldehyde
2,3-dimethylproponal
or
2,3-dimethylpropionaldehyde
78
Aldehydes and Ketones
Common names for aldehydes are derived from
the name of the acid with the same number of C
atoms.
IUPAC names are derived from the parent
hydrocarbon name by replacing -e with -al.
C
O
C
H
2
C
H
2
C
H
2
C H
3
H
C
O
C
C H
3
C H
3
CH
3
H
C
O
H
pentanal
or
pentyl aldehyde
2,3-dimethylproponal
or
2,3-dimethylpropionaldehyde
benzanal
or
benzyl aldehyde
79
Aldehydes and Ketones
The IUPAC name for a ketone is the characteristic
stem for the parent hydrocarbon plus the suffix -one.
A numeric prefix indicates the position of the
carbonyl group in a chain or on a ring.
C
O
C
H
2
C
H
2
C
H
2
C H
3
CH
3
2-hexanone
or
methyl pentyl ketone
80
Aldehydes and Ketones
The IUPAC name for a ketone is the characteristic
stem for the parent hydrocarbon plus the suffix -one.
A numeric prefix indicates the position of the
carbonyl group in a chain or on a ring.
C
O
C
H
2
C
H
2
C
H
2
C H
3
CH
3
2-hexanone
or
methyl pentyl ketone
C H
3
C
H
2
C
H
2
C
C
H
2
CH
3
O
3-hexanone
or
ethyl propyl ketone
81
Aldehydes and Ketones
The IUPAC name for a ketone is the characteristic
stem for the parent hydrocarbon plus the suffix -one.
A numeric prefix indicates the position of the
carbonyl group in a chain or on a ring.
C
O
C
H
2
C
H
2
C
H
2
C H
3
CH
3
2-hexanone
or
methyl pentyl ketone
C H
3
C
H
2
C
H
2
C
C
H
2
CH
3
O
3-hexanone
or
ethyl propyl ketone
C
CH
3
O
acetophenone
or
methyl phenyl ketone
82
Aldehydes and Ketones
Many aldehydes and ketones occur in nature.
C H
CH
C
O H
cinnamaldehyde
O
CH
3
CH
3
OH
testosterone
83
Amines
Amines are derivatives of ammonia in which one
or more H atoms have been replaced by organic
groups (aliphatic or aromatic or a mixture of
both).
There are three classes of amines.
H
N
H
H
ammonia
84
Amines
Amines are derivatives of ammonia in which one
or more H atoms have been replaced by organic
groups (aliphatic or aromatic or a mixture of
both).
There are three classes of amines.
H
N
H
H
C H
3
N
H
H
ammonia
primary
amine
85
Amines
Amines are derivatives of ammonia in which one
or more H atoms have been replaced by organic
groups (aliphatic or aromatic or a mixture of
both).
There are three classes of amines.
H
N
H
H
C H
3
N
H
H
C H
3
N
H
CH
3
ammonia
primary
amine
secondary
amine
86
Amines
Amines are derivatives of ammonia in which one
or more H atoms have been replaced by organic
groups (aliphatic or aromatic or a mixture of
both).
There are three classes of amines.
H
N
H
H
C H
3
N
H
H
C H
3
N
H
CH
3
C H
3
N
CH
3
CH
3
ammonia
primary
amine
secondary
amine
tertiary
amine
87
Amines
Aniline is the simplest aromatic amine. It is
much less basic than NH
3
.
Aniline is a very important industrial chemical.
88
Amines
Heterocylic amines have one or more N atoms
in a ring structure.
Many are important in living systems.
N
pyridine
89
Amines
Heterocylic amines have one or more N atoms
in a ring structure.
Many are important in living systems.
N
pyridine
N
N
pyrimidine
90
Amines
Heterocylic amines have one or more N atoms
in a ring structure.
Many are important in living systems.
N
pyridine
N
N
pyrimidine
N
N
N
N
purine
91
Carboxylic Acids
Carboxylic acids contain the carboxyl functional
group.
The general formula for carboxylic acids is:
R represents an alkyl or an aryl group
C
OH
O
R1
C
OH
O
92
Carboxylic Acids
IUPAC names for a carboxylic acid are derived
from the name of the parent hydrocarbon.
The final -e is dropped from the name of the
parent hydrocarbon
The suffix -oic is added followed by the word
acid.
Many organic acids are called by their common
(trivial) names which are derived from Greek or
Latin.
93
Carboxylic Acids
Positions of substituents on carboxylic acid chains
are indicated by numeric prefixes as in other
compounds
Begin the counting scheme from the carboxyl
group carbon atom.
They are also often indicated by lower case Greek
letters.
o = 1
st
C atom
| = 2
nd
C atom
= 3
rd
C atom, etc.
94
Carboxylic Acids
C
H C
OH
O
C H
3
CH
3
2-methylpropanoic acid
or
o-methylpropanoic acid
95
Carboxylic Acids
C
H C
OH
O
C H
3
CH
3
2-methylpropanoic acid
or
o-methylpropanoic acid
C H
3
C
H C
H
2
C
OH
O CH
3
3-methylbutanoic acid
or
|-methylbutanoic acid
96
Carboxylic Acids
C
H C
OH
O
C H
3
CH
3
2-methylpropanoic acid
or
o-methylpropanoic acid
C H
3
C
H C
H
2
C
OH
O CH
3
3-methylbutanoic acid
or
|-methylbutanoic acid
C H
3
C
H C
H
2
C
H
2
C
OH
O
CH
3
4-methylpentanoic acid
or
-methylpentanoic acid
97
Carboxylic Acids
Dicarboxylic acids contain two carboxyl groups per
molecule.
O H
C C
OH
O
O
oxalic acid
98
Nomenclature of Carboxylic
Acids
Dicarboxylic acids contain two carboxyl groups per
molecule.
O H
C C
OH O
O
O H
C
C
H
2
C
OH
O O
oxalic acid
malonic acid
99
Nomenclature of Carboxylic
Acids
Dicarboxylic acids contain two carboxyl groups per
molecule.
O H
C C
OH O
O
O H
C
C
H
2
C
OH
O O
O H
C
C
H
2
C
H
2
C
OH
O
O
oxalic acid
malonic acid
succinic acid
100

Carboxylic Acids
Aromatic acids are usually called by their
common names.
Sometimes, they are named as derivatives of
benzoic acid which is considered to be the
"parent" aromatic acid.

101
Carboxylic Acids
O O H
O O H
Cl
benzoic acid p-chlorobenzoic acid
102
Carboxylic Acids
O O H
O O H
Cl
O O H
CH
3
O
OH
O
OH
benzoic acid p-chlorobenzoic acid
p-toluic acid phthalic acid
103
Carboxylic Acids
Acid strengths of simple carboxylic acids vary
little with chain length.
However, substituents on a carbon atom in the
chain can cause large variations in acid
strengths .
104
Carboxylic Acids
C
OH
O
H
C H
3
C
OH
O
OH
C
C
H
2
C H
3
O
Compound Name
K
a
formic acid
acetic acid
propionic acid
1.8 x 10
-4
1.8 x 10
-5
1.4 x 10
-5
105
Carboxylic Acids
C
H
2
C
OH
O
Cl
Compound Name
K
a
monochloroacetic acid 1.5 x 10
-3
C H
3
C
OH
O
acetic acid 1.8 x 10
-5
C
H C
OH
O
Cl
Cl
dichloroacetic acid 5.0 x 10
-2
C
C
OH
O
Cl
Cl
Cl
trichloroacetic acid 2.0 x 10
-1
106
Carboxylic Acids
The -OH group in the carboxyl group of
carboxylic acids, is displaced in many of their
reactions.
The non -OH portion of a carboxylic acid is called
an acyl group.

R1
C
OH
O
R1
C
O
carboxyl group
acyl group
107
Some Derivatives of
Carboxylic Acids
Four important classes of compounds contain
acyl groups
They are all considered to be derivatives of
carboxylic acids.
In these structures R's may represent either
alkyl or aryl groups.
108
Some Derivatives of
Carboxylic Acids
R1
C
O
C
R1
O O
R1
C
Cl
O
acid anhydride acid chloride
109
Some Derivatives of
Carboxylic Acids
R1
C
O
C
R1
O O
R1
C
Cl
O
R1
C
O
R2
O
R1
C
NH
2
O
acid anhydride acid chloride
ester amide
110
Some Derivatives of
Carboxylic Acids
Acid anhydrides are related to their parent acids as
follows:
The word anhydride means without water.
C H
3
C
OH
O
2
C H
3
O CH
3
O O
+
H
2
O
acetic acid
acetic anhydride
111
Some Derivatives of
Carboxylic Acids
Acyl halides are much more reactive, and more
volatile, than their parent acids.
They react with water to form their parent acids and a
hydrohalic acid.
C H
3
C
Cl
O
C H
3
OH
O
+
HCl
acetyl chloride acetic acid
H
2
O
+
112
Some Derivatives of
Carboxylic Acids
Acyl halides are prepared by reacting their parent
acids with PCl
3
, PCl
5
, or SOCl
2
.
The more volatile acid halide is then distilled out of
the reaction mixture.
O O H
+
PCl
5
O Cl
benzoic acid benzoyl chloride
A
113
Some Derivatives of
Carboxylic Acids
Esters are prepared by heating a carboxylic acid with
an alcohol in the presence of a small amount of an
inorganic acid.
The reaction mixture will contain some ester and water, as
well as unreacted acid and alcohol.
C H
3
C
OH
O
C
H
2
OH C H
3
+
H
2
SO
4
C H
3
C
O
C
H
2
CH
3
O
+
H
2
O
ethanoic acid
or
acetic acid
ethanol
or
ethyl alcohol
ethyl ethanoate
or
ethyl acetate
114
Some Derivatives of
Carboxylic Acids
Esters are usually called by their common names.
Many simple esters occur naturally and have pleasant
odors.
Esters are frequently used in fragrances and as artificial
flavors.
C
H
2
C
O
C
H
2
CH
3
O
C
H
2
C H
3
ethyl butanoate
or
ethyl butyrate
odor of pineapples
C H
3
O
C
H
2
C
H
2
C
H
2
C
H
2
C
H
2
C
H
2
C
H
2
CH
3
O
octyl ethanoate
or
octyl acetate
odor of oranges
115
Some Derivatives of
Carboxylic Acids
Fats are solid esters of glycerol and (mostly) saturated
acids at room temperature.
Oils are liquid esters of glycerol and primarily
unsaturated acids at room temperature.
The "acid" parts of fats and oils usually contain even
numbers of C atoms in naturally occurring fats and oils.
16 and 18 carbon chains are the most commonly found
chain sizes in nature.
116
Some Derivatives of
Carboxylic Acids
Some acids that are found (as their esters) in fats
and oils include:
C H
3
C
H
2
C
H
2
C
H
2
C
H
2
C
H
2
C
H
2
C
H
2
C
H
2
C
H
2
C
H
2
C
H
2
C
H
2
C
H
2
C
H
2
C
OH
O
palmitic acid CH
3
(CH
2
)
14
COOH
117
Some Derivatives of
Carboxylic Acids
Stearic acid is often found in beef fat.
C H
3
C
H
2
C
H
2
C
H
2
C
H
2
C
H
2
C
H
2
C
H
2
C
H
2
C
H
2
C
H
2
C
H
2
C
H
2
C
H
2
C
H
2
C
H
2
C
H
2
C
OH
O
stearic acid CH
3
(CH
2
)
16
COOH
118
Some Derivatives of
Carboxylic Acids
Triglycerides are the triesters of glycerol.
The common name for triglycerides is tri (acid
stem) plus an -in suffix.
For example, tripalmitin.
119
Some Derivatives of
Carboxylic Acids
Waxes are esters of long chain fatty acids and
alcohols other than glycerol.
Commonly, waxes are derived from
monohydric alcohols.
Beeswax and carnauba wax are esters of myricyl
alcohol, C
30
H
61
OH.
120
Some Derivatives of
Carboxylic Acids
Carnauba wax is often used in car waxes.
carnauba wax
C
O
O
C
25
H
51
C
30
H
61
121
Some Derivatives of
Carboxylic Acids
Dihydric alcohols (2 OHs per molecule) can react
with dicarboxylic acids (2 COOHs per molecule) to
form polyesters.
Ester linkages are formed at both ends of both
molecules to give polymeric esters with very high
molecular weights.
C
OH
C
O H
O
O
+
C
H
2
C
H
2
OH O H
terephthalic acid
dicarboxylic acid
ethylene glycol
dihydric alcohol
122
Some Derivatives of
Carboxylic Acids
C
O
C
O
O
O
C H
2
CH
2
O
*
*
n
dacron
123
Some Derivatives of
Carboxylic Acids
Amides are derivatives of organic acids and primary
or secondary amines.
The functional groups of amides are:
C
N
O
R2
H
R1
C
N
O
R2
R3
R1
or
C
N
O
H
H
R1
or
124
Some Derivatives of
Carboxylic Acids
Amides are also named as derivatives of carboxylic
acids.
The suffix -amide is substituted for -ic acid or -oic
acid.
C
N
O
H
H
C H
3
C
NH
2
O
ethanamide
or
acetamide
benzamide
125
Some Derivatives of
Carboxylic Acids
When an aryl or alkyl substituent is present on the N
atom, the letter N and the name of the substituent are
prefixed to the name of the unsubstituted amide.
C
N
O
CH
3
H
C H
3
C
N O
CH
3
C H
2
CH
3
N-ethylethanamide
or
N-ethylacetamide
N-ethyl-N-methylbenzamide
126
Some Derivatives of
Carboxylic Acids
Acetaminophen Tylenol - is an amide.
127
Summary of the
Functional Groups
A summary of the functional groups is:
128
129
Substitution Reactions
In a substitution reaction an atom or group of
atoms attached to a carbon atom is replaced
(substituted for) by another atom or group of
atoms.
There is no change in the degree of saturation
at the reactive carbon atom.
Halogenation reactions are an important class
of substitution reactions.
Chlorine reacts with alkanes in free radical
chain reactions (also substitution reactions).
130
Substitution Reactions
Free radical chain reactions
The halogenation of methane is one example.
heat or
uv light
Cl

.
2
free radicals
Cl Cl

131
Substitution Reactions
Cl

.
+
H C
H
H

.
+

Cl

H
H C H
H
H

heat or
uv light
free radicals
Cl Cl

2 Cl

.
methyl radical
132
Substitution Reactions
H C
H
H

.
+
Cl Cl

+
Cl

.
H C
H
H

Cl

methyl radical
Cl

.
+
H C
H
H

.
+

Cl

H
H C H
H
H

heat or
uv light
free radicals
2 Cl

.
Cl Cl

methyl chloride
133
Substitution Reactions
Free radical chain reactions
Many substitution reactions of alkanes produce
more than one product.
C Cl H
H
H
+
Cl Cl C
H
H
Cl Cl
+
HCl
134
Substitution Reactions
C Cl H
H
H
+
Cl Cl C
H
H
Cl Cl
+
HCl
C
H
H
Cl Cl
+
Cl Cl C
H
Cl
Cl Cl
+
HCl
135
Substitution Reactions
HCl
C
H
Cl
Cl Cl
+
Cl Cl C
Cl
Cl
Cl Cl
+
HCl
C
H
H
Cl Cl
+
Cl Cl C
H
Cl
Cl Cl
+
C Cl H
H
H
+
Cl Cl C
H
H
Cl Cl
+
HCl
136
Substitution Reactions
Nitration reaction of an aromatic hydrocarbon
replaces an H atom attached to an aromatic ring
with a nitro, -NO
2
, group.
+
2
H SO
4
HNO
2
NO
2
137
Addition Reactions
An addition reaction involves an increase in
the number of groups attached to carbon.
The degree of saturation of the molecule is
increased.
C C
H
H H
H
+
Cl C C H
Cl
H
H H
Cl
2
138
Addition Reactions
Hydrogenation is a very important kind of addition reaction.
Hydrogenation is used to convert unsaturated fats and oils to
saturated fats or oils.
C C
H
H H
H
+
H C C H
H
H
H H
H
2
139
Elimination Reactions
An elimination reaction involves the removal
of groups attached to carbon.
The degree of unsaturation increases.
C C
C H
3
CH
3
H
H
C H
3
C H CH
Br
Br
CH
3
Zn in
acetic acid
or ethanol
C C
C H
3
H
CH
3
H
+
ZnBr
2
mixture of cis & trans-2-butene
+
140
Elimination Reactions
Dehydration is an important kind of
elimination reaction.
concentrated
2
H SO
4
C C
H
H
H
H
H
C H CH
OH
H
H
+
H O
2
141
Polymerization Reactions
A polymer is a large molecule that consists of
a high-molecular weight chain of small
molecules.
The small molecules that have been joined to form
the polymer are called monomers.
Synthetic polymers are a relatively new class
of molecules.
The first one, bakelite, was discovered in 1909.
Nylon, which is still extensively used, was
discovered in 1930s.
142
Polymerization Reactions
Addition polymerization is a large commercial
process in the United States.
Polyethylene is the addition polymer made in
the largest quantities in the United States.
Polyethylene is used to make Coke bottles, plastic
bags, etc.
143
Polymerization Reactions
Addition polymerization
Polyethylene formation
C H
2
CH
2
n
ethylene
catalyst
*
CH
2
CH
2
*
n
polyethylene
144
Polymerization Reactions
Addition polymerization
Teflon is the material used in nonstick frying pans
and other kitchen utensils.
C C
F
F F
F
n
catalyst
C C
F
F F
F
* *
n
polytetrafluoroethylene
or
Teflon
tetrafluoroethylene
heat
145
Polymerization Reactions
Formation of rubber
Natural rubber is a polymer made of isoprene (2-
methyl-1,3-butadiene) units that form a unique
stereoisomeric structure.
2n
natural rubber isoprene
C H
2
C C
H
CH
2
C H
3
CH
2
C
CH
C
H
2
CH
2
C
CH
CH
2
*
CH
3
CH
3
*
n
146
Polymerization Reactions
Vulcanization of rubber
Natural rubber is a sticky, soft compound when
heated which limited its commercial potential.
Charles Goodyear discovered in 1839 that heating
rubber with sulfur removed the stickiness and
made the substance elastic.
This is the basis of modern tire production.
Vulcanization provides disulfide cross-linking
bonds between the isoprene units.
147
Polymerization Reactions
Copolymers
If two different monomers are mixed and the
polymerized, copolymers are formed.
Styrene butadiene rubber - SBR - is an
important copolymer used in tire production.
148
Polymerization Reactions
Copolymers
3
styrene
butadiene
C C
C C
H
H
H
H
H
H
C
C H
H
H
+
149
Polymerization Reactions
CH
2
C
C
C H
2
CH
2
C
C
C
H
2
CH
2
C
C
H
2
C
C
CH
2
*
*
H
H
H
H
H
H
H
n
Styrene - butadiene rubber (SBR)
150
Polymerization Reactions
Condensation Polymers
Condensation polymers occur when two molecules
react and eliminate a small molecule.
Molecules eliminated commonly are water and HCl.
Important condensation polymers include nylon,
dacron, and kevlar.
Dacron is used in clothing to make it wrinkle free.
Blood does not clot in contact with dacron thus it is
used in artificial arteries.
151
Polymerization Reactions
Condensation Polymers
Dacron formation
terephthalic acid ethylene glycol
C
H
2
C
H
2
OH
O H
C
O O H
O OH
+
152
Polymerization Reactions
C
O
O
C
O
O C
H
2
C
H
2
C
H
2
O H
C
H
2
O H
n
Dacron is a polyester
+
H
2
O
153
Polymerization Reactions
Condensation Polymers
Nylon was first made by Wallace Carothers in
the 1930s.
Nylon is widely used in a variety of commercial
products including stockings, rope, guitar strings,
fire-proof clothing.
154
Polymerization Reactions
Condensation Polymers
Nylon 66 formation
O H
C
C
H
2
C
H
2
C
H
2
C
H
2
C
OH
O
O
N H
2
C
H
2
C
H
2
C
H
2
C
H
2
C
H
2
C
H
2
NH
2
+
adipic acid hexamethylene diamine
155
Polymerization Reactions
+
H
2
O
N H
2
C
C
H
2
C
H
2
C
H
2
C
H
2
C
N
H
C
H
2
C
H
2
C
H
2
C
H
2
C
H
2
C
H
2
N
H
C
OH
O
O
O
n
Nylon is a polyamide