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15-1
Organic Compounds and the Atomic Properties of Carbon
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
15-8
Figure 15.3 Some five-carbon skeletons.
15-9
Drawing Carbon Skeletons
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
15-12
Sample Problem 15.1 Drawing Hydrocarbons
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
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
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
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
15-17
Naming Organic Compounds
The name of any organic compound is comprised of three
portions:
PREFIX + ROOT + SUFFIX
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
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
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.
15-26
Chiral Molecules
15-27
Figure 15.8 An analogy for optical isomers.
15-28
Figure 15.9 Two chiral molecules.
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.
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.
15-32
Naproxen
15-33
Alkenes
15-34
Geometric Isomers
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
15-38
Sample Problem 15.2 Naming Alkanes, Alkenes, and Alkynes
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.
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
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
15-46
Tools of the Laboratory Nuclear Magnetic Resonance (NMR)
Spectroscopy
15-47
Types of Organic Reactions
R CH CH R + X Y R CH CH R
15-48
CH2 CH2 + H Cl H CH2 CH2 Cl
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
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
X Y
R CH CH R R CH CH R + X Y
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
R C X + Y R C Y + X
15-53
The main flavor ingredient in banana oil is formed through a
substitution reaction:
O CH3 O 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
15-55
Sample Problem 15.3
SOLUTION:
(a) CH3 CH2 CH2 Br CH3 CH CH2 + HBr
(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
15-56
Functional Groups
Organic compounds are classified according to their
functional groups, a group of atoms bonded in a
particular way.
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
15-60
Reactions of Alcohols
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
C X
15-63
Reactions of Haloalkanes
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
2-chloro-2-methylpropane
15-64
Figure 15.16 A tetrachlorobiphenyl, one of 209 polychlorinated
biphenyls (PCBs).
15-65
Amines
C N
15-66
Figure 15.17 General structures of amines.
15-67
Figure 15.18 Some biomolecules with the amine functional group.
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.
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
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
15-71
Alkenes
Alkenes contain the C=C double bond:
C C
OH
OH
2-methylpropene 2-methyl-2-propanol
15-72
Aromatic Hydrocarbons
Br
FeBr3
+ Br2 + HBr
benzene bromobenzene
15-73
Figure 15.19 The stability of benzene.
15-74
Aldehydes and Ketones
O O
R and R′ indicate
H C R R C R' hydrocarbon
aldehyde ketone groups.
15-75
Figure 15.20 Some common aldehydes and ketones.
15-76
Figure 15.21 The polar carbonyl group.
15-77
Reactions of Aldehydes and Ketones
O OH
cyclobutanone cyclobutanol
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
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
C OH
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.
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
15-83
Figure 15.23 Some lipid molecules with the ester functional
group.
Cetyl palmitate
The most common
lipid in whale
blubber
15-84
Saponification
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
C N
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
15-88
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
15-89
Figure 15.25 The formation of carboxylic, phosphoric, and sulfuric
acid anhydrides.
Sulfanilamide
Glucose-6-phosphate
15-91
Functional Groups with Triple Bonds
15-92
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
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
15-93
Polymers
15-94
Figure 15.27 Steps in the free-radical polymerization of ethylene.
15-95
Table 15.6 Some Major Addition Polymers
15-96
Table 15.6 Some Major Addition Polymers
15-97
Figure 15.28 The formation of nylon-66.
O O
O O
HO C (CH2)4 C NH (CH2)6 NH H
n
15-98
Figure 15.29 The structure of glucose in aqueous solution and the
formation of a disaccharide.
15-99
Figure 15.30 The common amino acids.
15-
Figure 15.30 The common amino acids.
15-
Figure 15.31 The structural hierarchy of proteins.
15-
Figure 15.32 The shapes of fibrous proteins.
collagen silk
fibroin
15-
Figure 15.33 Nucleic acid precursors and their linkage.
15-
Figure 15.34 The double helix of DNA and a section
showing base pairs.
15-
Figure 15.35 Key stages in protein synthesis.
15-
Figure 15.36 Key stages in DNA replication.
15-
Chemical Connections
Figure B15.5 Nucleoside triphosphate monomers.
15-
Chemical Connections
Figure B15.6 Steps in the Sanger method of DNA sequencing.
A. B.
C. D.
15-
Chemical Connections
Figure B15.7 STR analysis of DNA in the blood of seven suspects
and that in blood found at a crime scene.
15-