Beruflich Dokumente
Kultur Dokumente
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
2
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
3
Chapter Goals
Fundamental Classes of
Organic Reactions
16.Substitution Reactions
17.Addition Reactions
18.Elimination Reactions
19.Polymerization Reactions
4
Saturated Hydrocarbons
Hydrocarbons are chemical
compounds that contain only C and H
atoms.
Saturated hydrocarbons contain
only single or sigma () bonds.
There are no double or triple bonds in
these compounds.
The primary source of hydrocarbons
is petroleum and natural gas.
5
Alkanes and Cycloalkanes
The simplest saturated hydrocarbons
are called alkanes.
Methane, CH4, is the simplest alkane.
The alkanes form a homologous
series.
Each member of the series differs by
a specific number and kind of atoms.
H
C H or CH4
H
H
6
Alkanes and Cycloalkanes
The alkanes differ from each other by a CH2
or methylene group.
All alkanes have this general formula.
CnH2n+2
For example ethane, C2H6 , and propane,
C3H8 , are the next two family members.
H H H H H
H C C H H C C C H
H H H H H
H H
H C
H H
C2H6 H C
H H
C3H8
7
Alkanes and Cycloalkanes
Isomers are chemical compounds that
have the same molecular formulas but
different structures.
Two alkanes have the molecular formula C4H10.
They are a specific type of isomer called
structural isomers. H H H
H H H H
H C C C H
H C C C C H
H H
H H H H
H C H
H
H C
H H
n-butane H
H
H C
H H
2-methylpropane 8
Alkanes and Cycloalkanes
Three alkanes have the formula C5H12.
There are three structural isomers of pentane.
H2 H2
C C
H3C C CH3
H2
n-pentane
9
Alkanes and Cycloalkanes
Three alkanes have the formula C5H12.
There are three structural isomers of pentane.
H2 H2 CH3
C C C CH3
H3C C CH3 H3C H C
H2 H2
n-pentane 2-methylbutane
10
Alkanes and Cycloalkanes
Three alkanes have the formula C5H12.
There are three structural isomers of pentane.
H2 H2 CH3 CH3
C C CH CH3 C
H3C C CH3 H3C C H3C CH3
H2 H2 CH3
H H H
H C
H H
n-pentane H C
H H
2-methylbutane H C
H H
2,2-dimethylpropane
11
Alkanes and Cycloalkanes
There are five isomeric hexanes, C6H14.
You draw them!
H2 H2
C C CH3
H3C C C
H2 H2
n-hexane
12
Alkanes and Cycloalkanes
There are five isomeric hexanes, C6H14.
H2 H2 CH3 H2
C C CH3 C C
H3C C C H3C H C CH3
H2 H2 H2
n-hexane 2-methylpentane
13
Alkanes and Cycloalkanes
There are five isomeric hexanes, C6H14.
H2 H2 CH3 H2 H2 H2
C C CH3 C C C H C
H3C C C H3C H C CH3 H3C C CH3
H2 H2 H2 CH3
n-hexane 2-methylpentane 3-methylpentane
14
Alkanes and Cycloalkanes
There are five isomeric hexanes, C6H14.
H2 H2 CH3 H2 H2 H2
C C CH3 C C C H C
H3C C C H3C H C CH3 H3C C CH3
H2 H2 H2 CH3
n-hexane 2-methylpentane 3-methylpentane
CH3
C H2 CH3
H3C C
CH3
2,2-dimethylbutane
15
Alkanes and Cycloalkanes
There are five isomeric hexanes, C6H14.
H2 H2 CH3 H2 H2 H2
C C CH3 C C C H C
H3C C C H3C H C CH3 H3C C CH3
H2 H2 H2 CH3
n-hexane 2-methylpentane 3-methylpentane
CH3 CH3
C H2 CH3 C H CH3
H3C H C
H3C C
CH3 CH3
2,2-dimethylbutane 2,3-dimethylbutane
16
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.
17
Alkanes and Cycloalkanes
Cyclic saturated hydrocarbons are called
cycloalkanes.
They have the general formula CnH2n.
Some examples are:
H2
C
H2C CH2
C C
H2 H2
cyclopentane
18
Alkanes and Cycloalkanes
Cyclic saturated hydrocarbons are called
cycloalkanes.
They have the general formula CnH2n.
Some examples are:
H2 H2
C C
H2C CH2
H2C CH2
C C H2C CH2
C
H2 H2 H2
cyclopentane cyclohexane
19
Alkanes and Cycloalkanes
Cyclic saturated hydrocarbons are called
cycloalkanes.
They have the general formula CnH2n.
Some examples are:
H2 H2 H2
H2 C C
C C
H2C CH 2 H2C CH 2
H2C CH 2
H2C CH 2 H2C CH 2 H2C CH 2
C H2C CH 2
H2
H H H
H C
H H
cyclopentane H C
H H
cyclohexane H C
H H
cyclooctane
20
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
21
Naming Saturated Hydrocarbons
Number of carbon
atoms in chain Name
7 Heptane
8 Octane
9 Nonane
10 Decane
11 Unidecane
12 Dodecane
22
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.
23
Naming Saturated Hydrocarbons
25
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 CnH2n+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.
26
Unsaturated Hydrocarbons
27
Alkenes
The simplest alkenes contain one C=C bond per
molecule.
The general formula for simple alkenes is CnH2n.
The first two alkenes are:
ethene, C2H4
H H
C C
H
H C
H H
H H
28
Alkenes
The simplest alkenes contain one C=C bond per
molecule.
The general formula for simple alkenes is CnH2n.
The first two alkenes are:
and propene, C3H6
H
H
H C
C C
H
H
H C
H H
H H
29
Alkenes
Each doubly bonded C atom is sp2 hybridized.
The sp2 hybrid consists of:
two bonds (single bonds) and
one and one p bond (double bond)
30
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.
31
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.
32
Alkenes
H H
H
H C C H
C C C
C
H H H H
H
1,3-hexadiene
33
Alkenes
H H
H H H
H
H C C H
C C C H C C C
C C C C H
H H H H
H H H H
H H
H C
H H
1,3-hexadiene H C
H H
1,3,5-hexatriene
34
Alkenes
H H H H H
H
H C C H H C C C
C C C C C C H
C
H H H H
H H H H
1,3-hexadiene 1,3,5-hexatriene
H
H H C H H
H C C C
C C C H
H H H C H
H
2,3-dimethyl-1,3,5-hexatriene 35
Cycloalkenes
Cycloalkenes have the general formula CnH2n-2.
Examples are:
cyclopentene
H H
H
C
C C H
H
C C H
H H
36
Cycloalkenes
cyclohexene
H H
H
H C
C C H
CC H
H C
H
H H
37
Cycloalkenes
cycloheptene
H H
H H
H C C
C H
C
C H
H C C H
H H H
38
Alkynes
Alkynes contain CC bonds.
The simplest alkyne is C2H2, ethyne, or acetylene.
Alkynes with only one C C bond have the formula
CnH2n-2.
Each carbon atom in a C C bond is sp hybridized.
Each sp hybrid contains two bonds and two p 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.
H H H H H H H H H H H
H C C C C C C C H H C C C C C C C C H
H H H H H H H H H H H
H H
H C
H H
3-heptyne H C
H H
2-octyne
40
Alkynes
Acetylene is an important industrial chemical.
It is prepared by the reaction of calcium carbide
with water.
41
Alkynes
Acetylene burns in a highly exothermic reaction
The combustion produces temperatures of about 3000°C.
Acetylene is used in cutting torches for welding.
C2 H 2 g 2H 2 g C2 H 6 g
42
Hydrocarbons: A Summary
Carbon Atom
Hybridization C uses C forms Example
sp3 4
4 sp3 hybrids CH4
tetrahedral bonds
3
sp2 3 sp2 hybrids bonds C2H 4
trigonal planar & 1p orbital
1 p bond
2
2 sp hybrids bonds
sp linear C2H 2
& 2 p orbitals 2p
bonds
43
Aromatic Hydrocarbons
Historically, aromatic was used to describe
pleasant smelling substances.
Now it refers to benzene, C6H6, and derivatives
of benzene.
Other compounds that have similar chemical
properties to benzene are also called aromatic.
44
Benzene
The structure of benzene, C6H6, is:
H
H C H
C C
C C
H C H
H
H C
H H
H
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:
H H
napthalene
H C C H
C C C
C C C
H C C H
H
H C
H H
H H
46
Other Aromatic Hydrocarbons
phenanthrene
H
H C H
H C C
H C C C
C C C H
C C C
H C C 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
Other Aromatic Hydrocarbons
CH 3
CH 3 CH 3
CH 3
CH 3
CH 3
H
H C
H H m-xylene H
H
H C
H
o-xylene H
H C
H H
p-xylene
49
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.
50
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, CHCl3
Cl
C
Cl Cl
H
51
Organic Halides
1,2-dichloroethane, ClCH2CH2Cl
H Cl
H C C H
H
H C
H H
Cl H
52
Organic Halides
para-dichlorobenzene
Cl
Cl
53
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.
54
Alcohols and Phenols
Ethyl alcohol (ethanol), C2H5OH, is the most
familiar alcohol.
H H
H C C OH
H
H C
H H
H H
55
Alcohols and Phenols
Phenol, C6H5OH, is the most familiar phenol.
OH
56
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.
Ka 1.0 x 10-10 for phenol
Although phenols are very weakly acidic, they
are also very corrosive.
57
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.
H3C
C OH
H2
58
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:
H3C
HC OH
H3C
59
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
OH
H3C C CH3
CH3
60
Alcohols and Phenols
61
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.
H22 H222
H OH
OH H22
H H2 H2
C C
C C
C C
C C H C
H2C C CH333
CH H33C H C
C H C CH33 H3C C CH3
H22 H CH
OH H22
H OH
1-pentanol
1-pentanol 2-pentanol
2-pentanol 3-pentanol
1-pentyl alcohol 2-pentyl alcohol
2-pentyl alcohol 3-pentyl alcohol
62
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.
63
Alcohols and Phenols
OH
H2 H2
C C CH
HO C CH3 H3C CH 2
H2
CH 3
H H
H C
H H
1-butanol H C
H H
2-butanol
HO OH
CH 2
H3C C CH 3
CH
H3C CH 3 CH 3
H
H
H C
2-methyl-1-propanol
H C
H H
2-methyl-2-propanol
H H
64
Alcohols and Phenols
H2 H2 OH H2 H2 H2
There are eight isomericC five-carbon alcohols.
HO C C C H3C
C H C
C CH3
C C CH HC H C
3 CH
YouHdo it!
3 3
H H2 2 2 OH
1-pentanol 2-pentanol 3-pentanol
65
Alcohols and Phenols
glycerin sorbitol
66
Alcohols and Phenols
OH
OH
resorcinol
67
Alcohols and Phenols
OH OH
CH3
OH
resorcinol o-cresol
68
Alcohols and Phenols
OH OH OH
CH3
OH CH3
69
Alcohols and Phenols
OH CH3
CH3
resorcinol o-cresol m-cresol p-cresol
70
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).
71
Ethers
water
72
Ethers
water an alcohol
73
Ethers
O O O
H H H3C H H3C CH3
74
Ethers
O CH3 O H2 H2
H3C C H3C CH3 C C
H2 H3C O CH3
H
H H
H C ethylmethyl ether H C
H H
dimethyl ether H C
diethyl ether
H H H H
75
Aldehydes and Ketones
The functional group in aldehydes and ketones is
the carbonyl group.
R1 R2 or H
carbonyl group
76
Aldehydes and Ketones
Except for formaldehyde, aldehydes have one H
atom and one organic group bonded to a carbonyl
group.
O O O
H3C
H3C H H H C H
H2
ethanal methanal
H H
H propanal
H C
or H C or
H H H H H C
H H or
acetaldehyde formaldehyde
propionaldehyde
77
Aldehydes and Ketones
Ketones have two organic groups bonded to a
carbonyl group.
O O O
C C C
H3C CH 3 H2C CH 3 H2C CH 2
CH 3 CH 3 CH 3
H
propanone H 2-butanone H 3-pentanone
H C
H H
or H C
H H or H C
H H or
acetone ethylmethylketone diethylketone
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.
H2 O
H3C C C
C C H
H2 H2
pentanal
or
pentyl aldehyde
79
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.
O O
H2 H3C
H3C C C C
C C H C H
H2 H2 H3C
CH3
pentanal 2,3-dimethylproponal
or or
pentyl aldehyde 2,3-dimethylpropionaldehyde
80
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.
O O
H2 O
H3C C
H3C C C C
C H H
C C H
H2 H2 H3C
CH3
pentanal 2,3-dimethylproponal benzanal
or or or
pentyl aldehyde 2,3-dimethylpropionaldehyde benzyl aldehyde
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.
H2 O
H3C C C
C C CH3
H2 H2
2-hexanone
or
methyl pentyl ketone
82
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.
H2 O H2 O
H3C C C C C CH3
C C CH3 H3C C C
H2 H2 H2 H2
2-hexanone 3-hexanone
or or
methyl pentyl ketone ethyl propyl ketone
83
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.
O CH3
H2 O H2 O C
H3C C C C C CH3
C C CH3 H3C C C
H2 H2 H2 H2
cinnamaldehyde testosterone
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.
N
H H
H
ammonia
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.
N N
H H H3C H
H H
primary
ammonia
amine
87
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.
N N N
H H H3C H H3C H
H H CH3
primary secondary
ammonia
amine amine
88
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.
N N N N
H H H3C H H3C H H3C CH3
H H CH3 CH3
89
Amines
H C
H H
aniline
90
Amines
N
pyridine
91
Amines
N
N
pyridine pyrimidine
92
Amines
93
Carboxylic Acids
Carboxylic acids contain the carboxyl functional
group.
O
C
OH
The general formula for carboxylic acids is:
R represents an alkyl or an aryl group
O
C
R1 OH
94
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.
95
Carboxylic Acids
O
O
C
C H3C OH
H OH
methanoic acid H
ethanoic acid
H C
H
or H C
H H
or
H H
O O
H2
H 3C C C
C OH C
H2 H3C C OH
H2
H
propanoic acid butanoic acid
H C
H H
or H
H C or
propionic acid H H
butyric acid
96
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.
= 1st C atom
= 2nd C atom
= 3rd C atom, etc.
97
Carboxylic Acids
O
H3C H C
C OH
CH3
2-methylpropanoic acid
or
-methylpropanoic acid
98
Carboxylic Acids
O CH3 O
H3C H C C C
C OH H3C H C OH
CH3 H2
99
Carboxylic Acids
O CH3 O H2 O
H3C H C C C H3C H C C
C OH H3C H C OH C C OH
H2 H2
CH3 CH3
100
Carboxylic Acids
Dicarboxylic acids contain two carboxyl groups per
molecule.
O OH
C C
HO O
oxalic acid
101
Nomenclature of Carboxylic Acids
Dicarboxylic acids contain two carboxyl groups per
molecule.
O OH O O
C C C C
HO C OH
HO O H2
102
Nomenclature of Carboxylic Acids
Dicarboxylic acids contain two carboxyl groups per
molecule.
O O O H2
O OH
C C C C C C OH
HO C OH HO C C
HO O H2 H2
O
oxalic acid malonic acid succinic acid
103
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.
104
Carboxylic Acids
HO O
HO O
Cl
benzoic acid p-chlorobenzoic acid
105
Carboxylic Acids
HO O
HO O
Cl
benzoic acid p-chlorobenzoic acid
HO O
OH
O
OH
CH3 O
p-toluic acid phthalic acid
106
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 .
107
Carboxylic Acids
Compound Name Ka
O
C formic acid 1.8 x 10-4
H OH
O
C acetic acid 1.8 x 10-5
H3C OH
O
H3C C propionic acid 1.4 x 10-5
C OH
H2
108
Carboxylic Acids
Compound Name Ka
O
C acetic acid 1.8 x 10-5
H3C OH
O
Cl C monochloroacetic acid 1.5 x 10-3
C OH
H2
O
Cl H C dichloroacetic acid 5.0 x 10-2
C OH
Cl
O
Cl
C trichloroacetic acid 2.0 x 10-1
C OH
Cl
Cl
109
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.
O O
C C
R1 OH R1
carboxyl group acyl group
110
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.
111
Some Derivatives of
Carboxylic Acids
O O O
C C C
R1 O R1 R1 Cl
112
Some Derivatives of
Carboxylic Acids
O O O
C C C
R1 O R1 R1 Cl
O O
C R2 C
R1 O R1 NH2
ester amide
113
Some Derivatives of
Carboxylic Acids
Acid anhydrides are related to their parent acids as
follows:
The word anhydride means without water.
O O O
2 C + H2O
H3C OH H3C O CH3
114
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.
O O
C + H2O + HCl
H3C Cl H3C OH
115
Some Derivatives of
Carboxylic Acids
Acyl halides are prepared by reacting their parent acids
with PCl3, PCl5, or SOCl2.
The more volatile acid halide is then distilled out of the
reaction mixture.
HO O Cl O
+ PCl5
O H2SO4 O
H3C OH H2
C + C
H2 C C + H2O
H3C OH H3C O CH3
117
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.
H2 O H2 O H2 H2 H2 H2
C C C C C C C
H3C C O CH3 H3C O C C C CH3
H2 H2 H2 H2
119
Some Derivatives of
Carboxylic Acids
120
Some Derivatives of
Carboxylic Acids
Stearic acid is often found in beef fat.
H2 H2 H2 H2 H2 H2 H2 H2 O
C C C C C C C C C
H3C C C C C C C C C OH
H2 H2 H2 H2 H2 H2 H2 H2
121
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.
(CH2)14CH3
OH O C
H2C O
CH OH + 3 CH3(CH2)14COOH H 2C
HO CH 2 CH O
O CH 2 C (CH2)14CH3
O C O
glycerin palmitic acid
H
(CH2)14CH3
H C
H H
tripalmitin
122
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, C30H61OH.
123
Some Derivatives of
Carboxylic Acids
O
C C30H61
C25H51 O
carnauba wax
124
Some Derivatives of
Carboxylic Acids
Dihydric alcohols (2 –OH’s per molecule) can react
with dicarboxylic acids (2 –COOH’s per molecule) to
form polyesters.
Ester linkages are formed at both ends of both
molecules to give polymeric esters with very high
molecular weights.
O OH H2 H2
C C + C C
HO O HO OH
*
n
O O
* C CH2
O H2C
O
C
O
dacron
126
Some Derivatives of
Carboxylic Acids
Amides are derivatives of organic acids and primary or
secondary amines.
The functional groups of amides are:
O O O
C H or C R2 or C R2
R1 N R1 N R1 N
H H R3
127
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.
O NH2
O C
C H
H3C N
H
ethanamide benzamide
or
acetamide
128
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.
CH3
H2C
O N
O C CH3
C CH3
H3C N
H
N-ethylethanamide N-ethyl-N-methylbenzamide
or
N-ethylacetamide
129
Some Derivatives of
Carboxylic Acids
Acetaminophen – “Tylenol” - is an amide.
O
C
HN CH 3
OH
H
H C
H H
acetaminophen
130
Summary of the
Functional Groups
131
132
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).
133
Substitution Reactions
Free radical chain reactions
The halogenation of methane is one example.
heat or
·· ·· uv light ·· .
·· Cl ·· Cl ·· ·
2 · Cl
·· ·· ··
free radicals
134
Substitution Reactions
heat or
·· ·· uv light ··
·· Cl ·· Cl ·· 2 ·· Cl .
·· ·· ··
free radicals
H H
·· ·· . ·· . ··
·
H · C ·· H ·· Cl · ·· Cl ·· H
··
+ ··
H ·C
··
+ ··
H H
methyl radical
135
Substitution Reactions
heat or
·· ·· uv light ··
·· Cl ·· Cl ·· 2 ·· Cl .
·· ·· ··
free radicals
H H
·· ·· . ·· . ··
·
H · C ·· H ·· Cl · ·· Cl ·· H
··
+ ··
H ·C
··
+ ··
H H
methyl radical
H H
·· ·· ·· ·· ·· ·· .
H ·· C . + ·· Cl ·· Cl ·· H ·· C ·· Cl ·· + ·· Cl
·· ·· ·· ·· ·· ··
H H
methyl chloride
136
Substitution Reactions
Free radical chain reactions
Many substitution reactions of alkanes produce more
than one product.
H H
H C Cl + Cl Cl Cl C Cl + HCl
H H
137
Substitution Reactions
H H
H C Cl + Cl Cl Cl C Cl + HCl
H H
H H
Cl C Cl + Cl Cl Cl C Cl + HCl
H Cl
138
Substitution Reactions
H H
H C Cl + Cl Cl Cl C Cl + HCl
H H
H H
Cl C Cl + Cl Cl Cl C Cl + HCl
H Cl
H Cl
Cl C Cl + Cl Cl Cl C Cl + HCl
Cl Cl
139
Substitution Reactions
Nitration reaction of an aromatic hydrocarbon
replaces an H atom attached to an aromatic ring with
a nitro, -NO2, group.
NO
2
H2SO4
+ HNO
2
140
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.
H H H H
C C + Cl
2
H C C H
H H Cl Cl
141
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.
H H H H
C C + H
2
H C C H
H H H H
142
Elimination Reactions
An elimination reaction involves the removal of
groups attached to carbon.
The degree of unsaturation increases.
Br Br H H H CH3
Zn in
HC CH C C + C C + ZnBr
2
H3C CH3 acetic acid H C CH3 H3C H
or ethanol 3
143
Elimination Reactions
Dehydration is an important kind of elimination
reaction.
H OH H H
concentrated
HC CH C C + H2O
H H H SO4 H H
2
144
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 1930’s.
145
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.
146
Polymerization Reactions
Addition polymerization
Polyethylene formation
catalyst
n H2C CH2 CH2 CH2
* n *
ethylene polyethylene
147
Polymerization Reactions
Addition polymerization
Teflon is the material used in nonstick frying pans and
other kitchen utensils.
F F F F
catalyst
n C C * C C n *
heat
F F F F
tetrafluoroethylene polytetrafluoroethylene
or
Teflon
148
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.
H3C CH3 H CH3
H 2
2n C C C C C CH2 n *
H2C CH2 * CH2 CH CH2 CH
151
Polymerization Reactions
Copolymers
H
H H H C
C C H C H
3
H C C
+
H H
butadiene styrene
152
Polymerization Reactions
H
C H
* CH2 C
H2C H2 CH2 n *
CH2
C C
C C C C H
H C H2 CH2 H
H
H
153
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.
154
Polymerization Reactions
Condensation Polymers
Dacron formation
HO O
C
H2 H2
C C +
HO OH
O OH
ethylene glycol terephthalic acid
155
Polymerization Reactions
O O
H O C C O C C OC C O n
H + H2O
H2 H2 H2 H2
Dacron is a polyester
156
Polymerization Reactions
Condensation Polymers
Nylon was first made by Wallace Carothers in the
1930’s.
Nylon is widely used in a variety of commercial products
including stockings, rope, guitar strings, fire-proof
clothing.
157
Polymerization Reactions
Condensation Polymers
Nylon 66 formation
O H2 H2 H2 H2 H2
C C C OH C C C NH2
HO C C C + H2N C C C
H2 H2 H2 H2 H2
O
adipic acid hexamethylene diamine
158
Polymerization Reactions
O H2 H2 H2 H2 H2 O
H
C C C N C C C C
H2N C C C C C C N n OH + H2O
H2 H2 H2 H2 H2 H
O
Nylon is a polyamide
159
Synthesis Question
160
Synthesis Question
CH3
O N NO
2 2
NO
2
TNT or 2,4,6-trinitrotoluene
161
Group Question
Aerobic respiration produces carbon
dioxide and water as its end products.
Anaerobic respiration has different
end products. What are the end
products of anaerobic respiration?
How could you easily detect that
someone has switched from aerobic
to anaerobic respiration?
162
End of Chapter 27
There are more organic compounds
than any other type of chemical
species.
163