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Chapter 15

Organic Compounds and the


Atomic Properties of Carbon

15-1
Organic Compounds and the Atomic Properties of Carbon

15.1 The Special Nature of Carbon and the Characteristics of


Organic Molecules

15.2 The Structures and Classes of Hydrocarbons

15.3 Some Important Classes of Organic Reactions

15.4 Properties and Reactivities of Common Functional Groups

15.5 The Monomer-Polymer Theme I: Synthetic Macromolecules

15.6 The Monomer-Polymer Theme II: Biological Macromolecules

15-2
Bonding Properties of Carbon
• Carbon forms covalent bonds in all its elemental forms
and compounds.
– The ground state electron configuration of C is [He]2s22p2; the
formation of carbon ions is therefore energetically unfavorable.
– C has an electronegativity of 2.5, which is midway between that
of most metals and nonmetals. C prefers to share electrons.
• Carbon exhibits catenation, the ability to bond to itself
and form stable chain, ring, and branched compounds.
– The small size of the C atom allows it to form short, strong
bonds.
– The tetrahedral shape of the C atom allows catenation.

15-3
Figure 15.1 The position of carbon in the periodic table.

15-4
Comparison of Carbon and Silicon
• As atomic size increases down the group, bonds
between identical atoms become longer and weaker.
– A C–C bond is much stronger than a Si–Si bond.
• The bond energies of a C–C bond, a C–O bond, and a
C–Cl bond are very similar.
– C compounds can undergo a variety of reactions and remain
stable, while Si compounds cannot.
• Si has low energy d orbitals available for reaction,
allowing Si compounds to be more reactive than C
compounds.

15-5
Diversity and Reactivity of Organic Molecules
• Many organic compounds contain heteroatoms, atoms
other than C and H.
– The most common of these are O, N, and the halogens.
• Most reactions involve the interaction of electron rich
area in one molecule with an electron poor site in
another.
– C–C bonds and C–H bonds tend to be unreactive.
– Bonds between C and a heteroatom are usually polar, creating
an imbalance in electron density and providing a site for
reactions to occur.

15-6
Figure 15.2 Heteroatoms and different bonding arrangements
lead to great chemical diversity.
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

15-7
Carbon Skeletons

Each C atom can form a maximum of 4 bonds.


Groups joined by a single bond can rotate, so there are
often several different arrangements of a given carbon
skeleton that are equivalent:

15-8
Figure 15.3 Some five-carbon skeletons.

15-9
Drawing Carbon Skeletons

Each C atom can form a maximum of four bonds.


These may be four single bonds, OR one double and two single bonds,
OR one triple and one single bond.

The arrangement of C atoms determines the skeleton, so a


straight chain and a bent chain represent the same
skeleton.

Groups joined by a single bond can rotate freely, so a


branch pointing down is the same as one point up.

15-10
Figure 15.4 Adding the H-atom skin to the C-atom skeleton.

H H

C C H C C C

H H
A C atom single-bonded to one A C atom single-bonded to two
other atom gets three H atoms. other atoms gets two H atoms.

H
C
C C C
C C C
C
C
A C atom single-bonded to three
other atoms gets one H atom. A C atom single-bonded to four other atoms
is already fully bonded (no H atoms).

15-11
Figure 15.4 continued

H
H
C C H
C C C
A double-bonded C atom is
treated as if it were bonded to
two other atoms. C C H

A double- and single-bonded C


atom or a triple-bonded C atom is
treated as if it were bonded to three
other atoms.

15-12
Sample Problem 15.1 Drawing Hydrocarbons

PROBLEM: Draw structures that have different atom arrangements


for hydrocarbons with
(a) Six C atoms, no multiple bonds, and no rings
(b) Four C atoms, one double bond, and no rings
(c) Four C atoms, no multiple bonds, and one ring

PLAN: In each case, we draw the longest carbon chain first and
then work down to smaller chains with branches at
different points along them. Then we add H atoms to give
each C a total of four bonds.

15-13
Sample Problem 15.1

(a) Six carbons, no rings


H H H H H H H H H H H

H C C C C C C H H C C C C C H 5-C chain

H H H H H H H H H H
6-C chain H C H

H
H H H

H C H H C H H C H
H H H H H H H H H H

H C C C C C H H C C C C H H C C C C H

H H H H H H H H H H H
5-C chain H C H H C H
H H
4-C chains

15-14
Sample Problem 15.1

(b) Four C atoms, one double bond, and no rings

H H H H H H H H

H C C C C H H C C C C H

H H H H
4-C chains

H H

3-C chain H C C C H

H
H C H

15-15
Sample Problem 15.1

(c) Compounds with four C atoms and one ring

H H H H
C H
H C C H
H C C C H
H C C H
H H H
H H

15-16
Alkanes

Hydrocarbons contain only C and H.


Alkanes are hydrocarbons that contain only single bonds
and are referred to as saturated hydrocarbons.
The general formula for an alkane is CnH2n+2, where n is
any positive integer.
Alkanes comprise a homologous series, a group of
compounds in which each member differs from the next by
a –CH2– group.

15-17
Naming Organic Compounds
The name of any organic compound is comprised of three
portions:
PREFIX + ROOT + SUFFIX

The root name of the compound is determined from the


number of C atoms in the longest continuous chain.

The suffix indicates the type of organic compound, and is


placed after the root.
The suffix for an alkane is –ane.

The prefix identifies any groups attached to the main


chain.

15-18
Table 15.1 Numerical Roots for Carbon Chains and Branches

Roots Number of C
Atoms
meth- 1
eth- 2
prop- 3
but- 4
pent- 5
hex- 6
hept- 7
oct- 8
non- 9
dec- 10

15-19
Table 15.2 Rules for Naming an Organic Compound

15-20
Figure 15.5 Ways of depicting the alkane 3-ethyl-
H
2-methylhexane.

H C H CH3
H H H H H
CH3 CH CH CH2 CH2 CH3
H C C C C C C H
CH2
H H H H H
CH3
H C H
Condensed formula
H C H

H
Expanded formula

Carbon-skeleton formula Ball-and-stick model Space-filling model

15-21
Figure 15.6 Depicting cycloalkanes.
H H
H H
H C C H
C H
H
H C C H
C C
H H H H

Cyclobutane
Cyclopropan
e

15-22
Figure 15.6 Depicting cycloalkanes.
H H H H
H H C H
H C
C C C C
H H
H
C C H C C H
H C
H H H
H H
H H

Cyclopentane Cyclohexane

15-23
Constitutional Isomers

Constitutional or structural isomers have the same


molecular formula but a different arrangement of the
bonded atoms.

A straight-chain alkane may have many branched


structural isomers.

Structural isomers are different compounds and have


different properties.
If the isomers contain the same functional groups, their properties
will still be similar.

15-24
Table 15.3 The Constitutional Isomers of C4H10 and C5H12

15-25
Figure 15.7 Formulas, molar masses (in g/mol), structures, and
boiling points (at 1 atm pressure) of the first 10
unbranched alkanes.

Alkanes are nonpolar and their physical properties are


determined by the dispersion forces between their molecules.

15-26
Chiral Molecules

Stereoisomers are molecules with the same arrangement


of atoms but different orientations of groups in space.
Optical isomers are mirror images of each other that
cannot be superimposed.

A molecule must be asymmetric in order to exist as a pair


of optical isomers. An asymmetric molecule is termed
chiral.
Typically, a carbon atom is a chiral center if it is bonded to four different
groups.

15-27
Figure 15.8 An analogy for optical isomers.

If two compounds are mirror images of each other that cannot


be superimposed, they are called optical isomers.

15-28
Figure 15.9 Two chiral molecules.

optical isomers of 3- optical isomers of alanine


methylhexane

15-29
Optical Activity
A chiral compound is optically active; i.e., it rotates the
plane of polarized light.
A compound that rotates the plane of light clockwise is
called dextrorotatory, while a compound that rotates the
plane of light counterclockwise is called levorotatory.

Optical isomers have identical physical properties, except


that they rotate the plane of polarized light in opposite
directions.
In their chemical properties, optical isomers differ only in
a chiral (asymmetric) environment.

15-30
Figure 15.10 The rotation of plane-polarized light by an optically
active substance.

15-31
Figure 15.11 The binding site of an enzyme.

An enzyme provides a chiral environment and therefore distinguishes


one optical isomer from another. The shape of one optical isomer fits the
binding site, but the mirror image shape of the other isomer does not.

15-32
Naproxen

Many drugs are chiral molecules. One optical isomer has a


certain biological activity while the other has a different type
of activity or none at all.

15-33
Alkenes

A hydrocarbon that contains at least one C=C bond is


called an alkene.

Alkenes are unsaturated and have the general formula


CnH2n.

To name an alkene, the root name is determined by the


number of C atoms in the longest chain that also
contains the double bond.
The C chain is numbered from the end closest to the double bond.
The suffix for alkenes is –ene.

15-34
Geometric Isomers

The double bond of an alkene restricts rotation, so that


the relative positions of the atoms attached to the double
bond are fixed.
Alkenes may exist as geometric or cis-trans isomers,
which differ in the orientation of the groups attached to
the double bond.

Geometric isomers have different physical properties.

15-35
Table 15.4 The Geometric Isomers of 2-Butene

15-36
Figure 15.12 The initial chemical event in vision and the change in
the shape of retinal.

15-37
Alkynes

An alkyne is a hydrocarbon that contains at least one


CΞC triple bond.

Alkynes have the general formula CnH2n-2 and they are


also considred unsaturated carbons.

Alkynes are named in the same way as alkenes, using


the suffix –yne.

15-38
Sample Problem 15.2 Naming Alkanes, Alkenes, and Alkynes

PROBLEM: Give the systematic name for each of the following,


indicate the chiral center in part (d), and draw two
geometric isomers for part (e).
(a) CH3 (b) CH3 (c)
CH3 C CH2 CH3 CH3 CH2 CH CH CH3
CH3 CH2
(d) CH3
CH3 (e) CH3
CH3 CH2 CH CH CH2 CH3 CH2 CH C CH CH3
CH3

PLAN: For (a) to (c), we find the longest continuous chain (root) and
add the suffix –ane because there are only single bonds. Then
we name the branches, numbering the C chain from the end
closest to the first branch. For (d) and (e) the longest chain
must include the double bond.

15-39
Sample Problem 15.2

SOLUTION:
(a) methyl
CH3 methyl (b) CH3
methyl
CH3 C CH2 CH3 butane CH3 CH2 CH CH CH3
1 2 3 4 6 5 4 3
CH3 methyl 2 CH2

1 CH3
2,3-dimethylbutane
hexane
3,4-dimethylhexane
methyl
(c) 3
4 2
5 1
ethyl

1-ethyl-2-methylcyclopentane

15-40
Sample Problem 15.2

(d) methyl
CH3
CH3 CH2 CH CH CH2 1-pentene 3-methyl-1-pentene
5 4 3 2 1

chiral center

methyl methyl
(e) H CH3 CH3 CH2 CH3
C C 6 5 C C
CH3 CH2 4 3 CH CH3 H CH CH3 3-hexene
2 4 3
6 5 1 2
CH3 1
CH3
methyl methyl

cis-2,3-dimethyl-3-hexene trans-2,3-dimethyl-3-hexene

15-41
Figure 15.13 Representations of benzene.
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

or

Resonance forms
Resonance hybrid shows the
having alternating single
delocalized electrons as either
and double bonds.
an unbroken or a dashed circle.

Benzene is an aromatic hydrocarbon.

15-42
methylbenzene 1,2-dimethylbenzene 1,3-dimethylbenzene
(toluene) (o-xylene) (m-xylene)
bp = 110.6°C bp = 144.4°C bp = 139.1°C

O2N NO2

NO2

1,4-dimethylbenzene 2,4,6-trinitromethylbenzene
(p-xylene) (trinitrotoluene, TNT)
bp = 138.3°C
15-43
Tools of the Laboratory Nuclear Magnetic Resonance (NMR)
Spectroscopy

Figure B15.1 The basis of proton spin resonance.

15-44
Tools of the Laboratory Nuclear Magnetic Resonance (NMR)
Spectroscopy
Figure B15.2 The 1H-NMR spectrum of acetone.

15-45
Tools of the Laboratory Nuclear Magnetic Resonance (NMR)
Spectroscopy

Figure B15.3 The 1H-NMR spectrum of dimethoxymethane.

15-46
Tools of the Laboratory Nuclear Magnetic Resonance (NMR)
Spectroscopy

Figure B15.4 An MRI scan showing a brain tumor.

15-47
Types of Organic Reactions

An addition reaction occurs when an unsaturated reactant


becomes a saturated product:
X Y

R CH CH R + X Y R CH CH R

The C=C, CΞC, and C=O bonds commonly undergo


addition reactions.
In each case, it is the π bond that breaks, leaving the σ bond intact.

15-48
CH2 CH2 + H Cl H CH2 CH2 Cl
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Reactants (bonds broken) Products (bonds formed)


1 C=C = 614 kJ 1 C–C = -347 kJ
4 C–H = 1652 kJ 5 C–H = -2065 kJ
1 H–Cl = 427 kJ 1 C–Cl = -339 kJ
Total = 2693 kJ Total = -2751kJ

H°rxn = H°bonds broken + H°bonds formed = 2693 kJ + (-2751 kJ) = -58 kJ

15-49
Figure 15.14 A color test for C=C bonds.

Br2 (in pipet) reacts with a compound This compound has no C=C
that has a C=C bond, and the orange- bond, so the Br2 does not react.
brown color of Br2 disappears.
Br

C C + Br2 C C

Br
15-50
Types of Organic Reactions

An elimination reaction occurs when a saturated reactant


becomes an unsaturated product.
This reaction is the reverse of addition.

X Y

R CH CH R R CH CH R + X Y

The groups typically eliminated are H and a halogen atom


or H and an –OH group.

15-51
The driving force for an elimination reaction is the
formation of a small, stable molecule such as HCl (g) or
H2O.

OH H
H2SO4
R CH CH R R CH CH R + H OH
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

15-52
Types of Organic Reactions

A substitution reaction occurs when an atom or group


from an added reagent substitutes for one attached to a
carbon in the organic reagent.

R C X + Y R C Y + X

The C atom at which substitution may be saturated or


unsaturated, and X and Y can be many different atoms.

15-53
The main flavor ingredient in banana oil is formed through a
substitution reaction:

O CH3 O CH3

CH3 C Cl + HO CH2 CH2 CH CH3 CH3 C O CH2 CH2 CH CH3

+ H Cl
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

15-54
Sample Problem 15.3 Recognizing the Type of Organic
Reaction
PROBLEM: State whether each reaction is an addition, elimination,
or substitution:
(a) CH3 CH2 CH2 Br CH3 CH CH2 + HBr

(b) + H2
O O
(c) CH3 C Br + CH3CH2OH CH3 C OCH2CH3 + HBr

PLAN: We determine the type of reaction by looking for any


change in the number of atoms bonded to C.
• An addition reaction results in more atoms bonded to C.
• An elimination reaction results in fewer atoms bonded to C.
•If there are the same number of atoms bonded to C, the
reaction is a substitution.

15-55
Sample Problem 15.3
SOLUTION:
(a) CH3 CH2 CH2 Br CH3 CH CH2 + HBr

This is an elimination reaction; two bonds in the reactant, C–H and


C –Br, are absent in the product.

(b) + H2

This is an addition reaction; two more C–H bonds have formed in the
product.
O O
(c) CH3 C Br + CH3CH2OH CH3 C OCH2CH3 + HBr

This is a substitution reaction; the reactant C–Br bond has been


replaced by a C–O bond in the product.

15-56
Functional Groups
Organic compounds are classified according to their
functional groups, a group of atoms bonded in a
particular way.

The functional groups in a compound determine both its


physical properties and its chemical reactivity.
Functional groups affect the polarity of a compound, and therefore
determine the intermolecular forces it exhibits.
Functional groups define the regions of high and low electron density in
a compound, thus determining its reactivity.

15-57
Table 15.5 Important Functional Groups in Organic Compounds

15-58
Table 15.5 Important Functional Groups in Organic Compounds

15-59
Alcohols

The alcohol functional group consists of a carbon bonded


to an –OH group.
C O H

Alcohols are named by replacing the –e at the end of the


parent hydrocarbon name with the suffix –ol.

Alcohols have high melting and boiling points since they


can form hydrogen bonds between their molecules.

15-60
Reactions of Alcohols

Alcohols undergo elimination and substitution reactions.


OH

H+
+ H2O dehydration (elimination)

cyclohexanol cyclohexene

OH O
K2Cr2O7
CH3 CH2 CH CH3 CH3 CH2 C CH3
H2SO4
oxidation OH O
(elimination)
2-butanol 2-butanone

15-61
Figure 15.15 Some molecules with the alcohol functional group.

15-62
Haloalkanes

Haloalkanes or alkyl halides contain a halogen atom


bonded to carbon.

C X

Haloalkanes are named by identifying the halogen with a


prefix on the hydrocarbon name. The C bearing the
halogen must be numbered.

15-63
Reactions of Haloalkanes

Haloalkanes undergo substitution and elimination reactions.

CH3 CH2 CH2 CH2 Br + OH- CH3 CH2 CH2 CH2 OH + Br-
1-bromobutane 1-butanol

CH3 CH3
- +
CH3 C CH3 + CH3 CH2 O K CH3 C CH2 + KCl + CH3 CH2 OH

Cl potassium ethoxide 2-methylpropene ethanol

2-chloro-2-methylpropane

15-64
Figure 15.16 A tetrachlorobiphenyl, one of 209 polychlorinated
biphenyls (PCBs).

15-65
Amines

The amine functional group contains a N atom.

C N

The systematic name for an amine is formed by dropping


the final –e of the alkane and adding the suffix –amine.

Common names that use the name of the alkyl group


followed by the suffix –amine are also widely used.
CH3CH2NH2 CH3CH2 NH CH2CH3
ethanamine OR diethylamine
ethylamine

15-66
Figure 15.17 General structures of amines.

Amines are classified according to the number of R groups directly


attached to the N atom.

15-67
Figure 15.18 Some biomolecules with the amine functional group.

Lysine (1° amine) Adenine (1° amine)


amino acid found component of
in proteins nucleic acids

Epinephrine
(adrenaline; 2° amine) Cocaine (3° amine)
neurotransmitter in brain stimulant;
brain; hormone released widely abused drug
during stress

15-68
Properties and Reactions of Amines
Primary and secondary amines can form H bonds;
therefore they have higher melting and boiling points than
hydrocarbons or alkyl halides of similar mass.

Tertiary amines cannot form H bonds between their


molecules because they lack a polar N–H bond.

Amines of low molar mass are fishy smelling, water


soluble, and weakly basic.

Amines undergo a variety of reactions, including


substitution reactions.

15-69
Sample Problem 15.4 Predicting the Reactions of Alcohols,
Alkyl Halides, and Amines
PROBLEM: Determine the reaction type and predict the product(s)
for each reaction:
(a) CH3 CH2 CH2 I + NaOH
(b) CH3 CH2 CH2 Br + 2 CH3 CH2 CH2 NH2
Cr2O72-
(c) CH3 CH CH3
H2SO4
OH

PLAN: We first determine the functional group(s) of the reactant(s)


and then examine any inorganic reagent(s) to decide on the
reaction type. Keep in mind that, in general, these functional
groups undergo substitution or elimination.

15-70
Sample Problem 15.4

SOLUTION:
(a) In this reaction the OH of the NaOH reaction substitutes for the I
in the organic reagent:
CH3 CH2 CH2 OH + NaI

(b) This is a substitution reaction:


CH3 CH2 CH2 NH + CH3 CH2 CH2 NH2Br
CH2CH3

(c) This is an elimination reaction since acidic Cr2O72- is a strong


oxidizing agent:
CH3 C CH3
O

15-71
Alkenes
Alkenes contain the C=C double bond:

C C

Alkenes typically undergo addition reactions.


The electron-rich double bond is readily attracted to the partially
positive H atoms of H3O+ ions and hydrohalic acids.
CH3 CH3

CH3 C CH2 + H3O+ CH3 C CH3 + H+

OH
OH

2-methylpropene 2-methyl-2-propanol
15-72
Aromatic Hydrocarbons

Benzene is an aromatic hydrocarbon and is a resonance


hybrid. Its  bond electrons are delocalized.

Aromatic compounds are unusually stable and although


they contain double bonds they undergo substitution rather
than addition reactions.

Br
FeBr3
+ Br2 + HBr

benzene bromobenzene

15-73
Figure 15.19 The stability of benzene.

Benzene releases less energy


during hydrogenation than expected,
because it is already much more
stable than a similar imaginary
alkene.

15-74
Aldehydes and Ketones

Aldehydes and ketones both contain the carbonyl


group, C=O.

O O
R and R′ indicate
H C R R C R' hydrocarbon
aldehyde ketone groups.

Aldehydes are named by replacing the final –e of the


alkane name with the suffix –al.
Ketones have the suffix –one and the position of the
carbonyl must always be indicated.

15-75
Figure 15.20 Some common aldehydes and ketones.

Methanal (formaldehyde) Used


to make resins in plywood, Benzaldehyde
dishware, countertops; Artificial almond
biological preservative flavoring

Ethanal (acetaldehyde) 2-Propanone (acetone) 2-Butanone


Narcotic product of ethanol Solvent for fat, rubber, plastic, (methyl ethyl ketone)
metabolism; used to make varnish, lacquer; chemical Important solvent
perfumes, flavors, plastics, feedstock
other chemicals

15-76
Figure 15.21 The polar carbonyl group.

The C=O bond is electron rich and is also highly polar. It


readily undergoes addition reactions, and the electron-poor C
atom attracts electron-rich groups.

15-77
Reactions of Aldehydes and Ketones

Reduction to alcohols is an example of an addition reaction:


reduction

O OH
cyclobutanone cyclobutanol

Organometallic compounds, which have a metal atom


covalently bonded to C, add to the electron-poor carbonyl C:
-
O OH
- +
R C H + R' Li R CH R' + LiOH
+

15-78
Sample Problem 15.5 Predicting the Steps in a Reaction
Sequence
PROBLEM: Fill in the blanks in the following reaction sequence:
Br
- Cr2O72- CH3-Li
OH H2O
CH3 CH2 CH CH3
H2SO4

PLAN: For each step we examine the functional group of the


reactant and the reagent above the yield arrow to decide on
the most likely product.

SOLUTION: The first step involves an alkyl halide reacting with OH-,
so this is probably a substitution reaction, which yields
an alcohol. In the next step the alcohol is oxidized to a
ketone and finally the organometallic reagent adds to the
ketone to give an alcohol with one more C in its skeleton:

15-79
Sample Problem 15.5

Br OH Cr2O72-
O
-
OH
CH3 CH2 CH CH3 CH3 CH2 CH CH3 CH3 CH2 C CH3
H2SO4
substitution oxidation
CH3-Li
(elimination)
addition
H2O

OH
CH3 CH2 C CH3
CH3

15-80
Carboxylic Acids

Carboxylic acids contain the functional group –COOH, or


O

C OH

Carboxylic acids are named by replacing the –e of the


alkane with the suffix –oic acid.

Carboxylic acids are weak acids in water, and react with


strong bases:
O O

CH3 C OH (l) + NaOH (aq) CH3 C O- (aq) + Na+ (aq) + H2O (l)
methanoic acid methanoate anion

15-81
Figure 15.22 Some molecules with the carboxylic acid functional
group.

Methanoic acid (formic acid) Butanoic acid (butyric acid)


An irritating component of ant and Odor of rancid butter; suspected
bee stings component of monkey sex
attractant

Benzoic acid
Calorimetric standard; used in
preserving food, dyeing fabric, Octadecanoic acid (stearic acid)
curing tobacco Found in animal fats; used in making
candles and soaps
15-82
Esters

The ester group is formed by the reaction of an alcohol and a


carboxylic acid.
O O

CH3 C OH + H O CH3 CH3 C O CH3 + HOH

ethanoic acid methanol methyl ethanoate

Esterification is a dehydration-condensation reaction.

Ester groups occur commonly in lipids, which are formed by


the esterification of fatty acids.

15-83
Figure 15.23 Some lipid molecules with the ester functional
group.

Cetyl palmitate
The most common
lipid in whale
blubber

Tristearin Typical dietary fat


used as an energy store in
animals
Lecithin Phospholipid found in all cell
membranes

15-84
Saponification

Ester hydrolysis can be carried out using either aqueous


acid or aqueous base. When base is used the process is
called saponification.
This is the process used to make soaps from lipids.

O O
R C O CH2 R C O- Na+ HO CH2
O 3NaOH O
R' C O CH  R' C O- Na+ HO CH
O O
R" C O CH2 R" C O- Na+ HO CH2
a triglyceride 3 soaps glycerol
(salts of fatty acids)

15-85
Amides

An amide contains the functional group:


O

C N

Amides, like esters, can be hydrolyzed to give a


carboxylic acid and an amine.

The peptide bond, which links amino acids in a protein,


is an amide group.

15-86
Figure 15.24 Some molecules with the amide functional group.

Acetaminophen
Active ingredient in nonaspirin
pain relievers; used to make dyes
and photographic chemicals

N,N-Dimethylmethanamide
Lysergic acid diethylamide (LSD-25)
(dimethylformamide)
A potent hallucinogen
Major organic solvent; used in
production of synthetic fibers

15-87
Sample Problem 15.6 Predicting the Reactions of the Carboxylic
Acid Family

PROBLEM: Predict the product(s) of the following reactions:


O OH
H+
(a) CH3 CH2 CH2 C OH + CH3 CH CH3
CH3 O
NaOH
(b) CH3 CH CH2 CH2 C NH CH2CH3
H2O

PLAN: We identify the functional groups in the reactant(s) and see


how they change. In (a), a carboxylic acid reacts with an
alcohol, so the reaction must be a substitution to form an
ester. In (b), an amide reacts with aqueous base, so
hydrolysis occurs.

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Sample Problem 15.6

SOLUTION:
O OH O CH3
H+
(a) CH3 CH2 CH2 C OH + CH3 CH CH3 CH3 CH2 CH2 C O CH CH3
+ H2O

CH3 O CH3 O
NaOH
(b) CH3 CH CH2 CH2 C NH CH2CH3 CH3 CH CH2 CH2 C O- Na+
H2O
+
NH2 CH2CH3

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Figure 15.25 The formation of carboxylic, phosphoric, and sulfuric
acid anhydrides.

P and S form acids, anhydrides and esters that


are analogous to organic compounds.
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Figure 15.26 A phosphate ester and a sulfonamide.

Sulfanilamide
Glucose-6-phosphate

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Functional Groups with Triple Bonds

Alkynes contain the electron rich –CΞC– group, which


readily undergoes addition reactions:
H2 H2
CH3 C CH CH3 CH CH2 CH3 CH2 CH3
propyne propene propane

Nitriles contain the group –CΞN and are made by a


substution reaction of an alkyl halide with CN- (cyanide):

CH3 CH2 Cl + NaCN CH3 CH2 C N + NaCl

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Sample Problem 15.7 Recognizing Functional Groups

PROBLEM: Circle and name the functional groups in the following molecules:
O
(a) (b) OH (c) O
C OH O
CH CH2 NH CH3
O C CH3

Cl

PLAN: Use Table 15.5 to identify the various functional groups.

SOLUTION:
carboxylic acid alcohol
O
(a) ester (b) OH
(c) O
ketone
C OH O
CH CH2 NH CH3
O C CH3
2° amine Cl
aromatic ring alkene
haloalkane
aromatic ring

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Polymers

Addition polymers, also called chain-growth polymers


form when monomers undergo an addition reaction with
each other.
The monomers of most addition polymers contain an alkene group.

Condensation polymers are formed when monomers link


by a dehydration-condensation type reaction.
The monomers of condensation polymers have two functional groups,
and each monomer can link to two others.

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Figure 15.27 Steps in the free-radical polymerization of ethylene.

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Table 15.6 Some Major Addition Polymers

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Table 15.6 Some Major Addition Polymers

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Figure 15.28 The formation of nylon-66.

O O

HO C (CH2)4 C OH + nH2N (CH2)6 NH2

O O

HO C (CH2)4 C NH (CH2)6 NH H
n

Nylon-66 is a condensation polymer,


made by reacting a diacid with a
diamine. The polyamide forms
between the two liquid phases.

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Figure 15.29 The structure of glucose in aqueous solution and the
formation of a disaccharide.

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Figure 15.30 The common amino acids.

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Figure 15.30 The common amino acids.

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Figure 15.31 The structural hierarchy of proteins.

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Figure 15.32 The shapes of fibrous proteins.

collagen silk
fibroin

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Figure 15.33 Nucleic acid precursors and their linkage.

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Figure 15.34 The double helix of DNA and a section
showing base pairs.

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Figure 15.35 Key stages in protein synthesis.

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Figure 15.36 Key stages in DNA replication.

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Chemical Connections
Figure B15.5 Nucleoside triphosphate monomers.

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Chemical Connections
Figure B15.6 Steps in the Sanger method of DNA sequencing.

A. B.

C. D.

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Chemical Connections
Figure B15.7 STR analysis of DNA in the blood of seven suspects
and that in blood found at a crime scene.

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