Organic chemistry principles and mechanisms 2e by joel karty 1

Organic Chemistry
Principles and Mechanisms
s eco n d e d i t i o n

Joel M. Karty
Elon University

n

W. W. N o r t o n
N e w yo r k • L o n d o n


To Pnut, Fafa, and Jakers

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Names: Karty, Joel, author.
Title: Organic chemistry : principles and mechanisms / Joel M. Karty, Elon
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About the Author
JOE L KARTY earned his B.S. in chemistry at the University of

Puget Sound and his Ph.D. at Stanford University. He joined the
faculty of Elon University in 2001, where he currently holds the
rank of full professor. He teaches primarily the organic chemistry

sequence and also teaches general chemistry. In the summer, Joel
teaches at the Summer Biomedical Sciences Institute through the
Duke University Medical Center. His research interests include in-

vestigating the roles of resonance and inductive effects in funda-

mental chemical systems and studying the mechanism of pattern

formation in Liesegang reactions. He has written a very successful
student supplement, Get Ready for Organic Chemistry, Second Edition (formerly called The Nuts and Bolts of Organic Chemistry).

   iii



Brief Contents
1  ​Atomic and Molecular Structure  1
Interchapter A  ​Nomenclature: The Basic
System for Naming Organic Compounds: Alkanes,
Haloalkanes, Nitroalkanes, Cycloalkanes, and
Ethers  52

10  ​Nucleophilic Substitution and Elimination
Reactions 2: Reactions That Are Useful for
Synthesis  515
11  ​Electrophilic Addition to Nonpolar π Bonds 1:
Addition of a Brønsted Acid  563

2  ​Three-Dimensional Geometry, Intermolecular
Interactions, and Physical Properties  70

12  ​Electrophilic Addition to Nonpolar π Bonds 2:
Reactions Involving Cyclic Transition States  601

3  ​Orbital Interactions 1: Hybridization and

13  ​Organic Synthesis 1: Beginning Concepts in

Two-Center Molecular Orbitals  119

Designing Multistep Synthesis  641

Interchapter B  ​Naming Alkenes, Alkynes, and
Benzene Derivatives  152

14  ​Orbital Interactions 2: Extended π Systems,
Conjugation, and Aromaticity  682

4  ​Isomerism 1: Conformers and Constitutional
Isomers  165

15  ​Structure Determination 1: Ultraviolet–Visible

and Infrared Spectroscopies  723

5  ​Isomerism 2: Chirality, Enantiomers, and
Diastereomers  208

16  ​Structure Determination 2: Nuclear
Magnetic Resonance Spectroscopy and Mass
Spectrometry  771

Interchapter C  ​Stereochemistry in
Nomenclature: R and S Configurations about
Asymmetric Carbons and Z and E Configurations
about Double Bonds  258

17  ​Nucleophilic Addition to Polar π Bonds 1:
Addition of Strong Nucleophiles  839

6  ​The Proton Transfer Reaction: An Introduction
to Mechanisms, Thermodynamics, and Charge
Stability  274

Nucleophiles and Acid and Base Catalysis  888

7  ​An Overview of the Most Common Elementary
Steps  328
Interchapter D  ​Molecular Orbital Theory,
Hyperconjugation, and Chemical Reactions  364

Interchapter E  ​Naming Compounds with
a Functional Group That Calls for a Suffix 1:

Alcohols, Amines, Ketones, and Aldehydes  377
8  ​An Introduction to Multistep Mechanisms: SN1
and E1 Reactions and Their Comparisons to SN2
and E2 Reactions  393

18  ​Nucleophilic Addition to Polar π Bonds 2: Weak
19  ​Organic Synthesis 2: Intermediate Topics in
Synthesis Design, and Useful Redox and
Carbon–Carbon Bond-Forming Reactions  946
20  ​Nucleophilic Addition–Elimination Reactions
1: The General Mechanism Involving Strong
Nucleophiles  1000
21  ​Nucleophilic Addition–Elimination Reactions 2:
Weak Nucleophiles  1045
22  ​Aromatic Substitution 1: Electrophilic Aromatic
Substitution on Benzene; Useful Accompanying
Reactions  1104

9  ​Nucleophilic Substitution and Elimination

23  ​Aromatic Substitution 2: Reactions of
Substituted Benzenes and Other Rings  1144

Reactions 1: Competition among SN2, SN1, E2, and
E1 Reactions  442

24  ​The Diels–Alder Reaction and Other Pericyclic
Reactions  1198

Interchapter F  ​Naming Compounds with

a Functional Group That Calls for a Suffix 2:
Carboxylic Acids and Their Derivatives  503

25  ​Reactions Involving Free Radicals  1247
Interchapter G  Fragmentation Pathways in Mass
Spectrometry  1295

26  Polymers 

1307
   v



Contents
List of Biochemistry Topics xxiii
List of Interest Boxes xxv
List of Connections Boxes xxvi
List of Green Chemistry Boxes xxix
List of Mechanisms xxx
Preface xxxiii

1 Atomic and Molecular Structure

 1

1.1What Is Organic Chemistry? 1
1.2Why Carbon? 3
1.3Atomic Structure and Ground State Electron Configurations 4
1.4The Covalent Bond: Bond Energy and Bond Length 8

1.5Lewis Dot Structures and the Octet Rule 12
1.6Strategies for Success: Drawing Lewis Dot Structures Quickly 14
1.7Electronegativity, Polar Covalent Bonds, and Bond Dipoles 16
1.8Ionic Bonds 18
1.9Assigning Electrons to Atoms in Molecules: Formal Charge 19
1.10 Resonance Theory 21
1.11 Strategies for Success: Drawing All Resonance Structures 25
1.12 Shorthand Notations 30
1.13 An Overview of Organic Compounds: Functional Groups 34

THE ORGANIC CHEMISTRY OF BIOMOLECULES
1.14 An Introduction to Proteins, Carbohydrates, and Nucleic Acids:
Fundamental Building Blocks and Functional Groups 37

Chapter Summary and Key Terms 45

Problems 45
INTERCHAPTER

A

Nomenclature: The Basic System
for Naming Organic Compounds
Alkanes, Haloalkanes, Nitroalkanes, Cycloalkanes,
and Ethers 52

A.1The Need for Systematic Nomenclature: An Introduction to
the IUPAC System 52
   vii

A.2Alkanes and Substituted Alkanes 53
A.3Haloalkanes and Nitroalkanes: Roots, Prefixes, and Locator Numbers 54
A.4Alkyl Substituents: Branched Alkanes and Substituted Branched
Alkanes 58
A.5Cyclic Alkanes and Cyclic Alkyl Groups 60
A.6Ethers and Alkoxy Groups 62
A.7Trivial Names or Common Names 63

Problems 67

2

Three-Dimensional Geometry,
Intermolecular Interactions, and
Physical Properties 70

2.1Valence Shell Electron Pair Repulsion (VSEPR) Theory:
Three-Dimensional Geometry 71
2.2Dash–Wedge Notation 75
2.3Strategies for Success: The Molecular Modeling Kit 77
2.4Net Molecular Dipoles and Dipole Moments 78
2.5Physical Properties, Functional Groups, and Intermolecular
Interactions 80
2.6Melting Points, Boiling Points, and Intermolecular Interactions 82
2.7Solubility 91
2.8Strategies for Success: Ranking Boiling Points and Solubilities of
Structurally Similar Compounds 96
2.9Protic and Aprotic Solvents 99
2.10 Soaps and Detergents 101

THE ORGANIC CHEMISTRY OF BIOMOLECULES
2.11 An Introduction to Lipids 105

Chapter Summary and Key Terms 112

Problems 113

3

Orbital Interactions 1
Hybridization and Two-Center Molecular Orbitals 119

3.1Atomic Orbitals and the Wave Nature of Electrons 120
3.2Interaction between Orbitals: Constructive and Destructive
Interference 122
3.3An Introduction to Molecular Orbital Theory and σ Bonds: An Example
with H2 124
3.4Hybrid Atomic Orbitals and Geometry 128
3.5Valence Bond Theory and Other Orbitals of σ Symmetry:
An Example with Ethane (H3C i CH3) 133
3.6An Introduction to π Bonds: An Example with
Ethene (H2C w CH2) 136
viii   Contents


3.7Nonbonding Orbitals: An Example with Formaldehyde (H2C w O) 139
3.8Triple Bonds: An Example with Ethyne (HC { CH) 140
3.9Bond Rotation about Single and Double Bonds: Cis and
Trans Configurations 141

3.10 Strategies for Success: Molecular Models and Extended Geometry
about Single and Double Bonds 144
3.11 Hybridization, Bond Characteristics, and Effective
Electronegativity 145

Chapter Summary and Key Terms 148

Problems 149
INTERCHAPTER

B

Naming Alkenes, Alkynes, and Benzene
Derivatives 152

B.1Alkenes, Alkynes, Cycloalkenes, and Cycloalkynes: Molecules with
One C w C or C { C 152
B.2Molecules with Multiple C w C or C { C Bonds 155
B.3Benzene and Benzene Derivatives 157
B.4Trivial Names Involving Alkenes, Alkynes, and Benzene
Derivatives 159

Problems 162

4

Isomerism 1
Conformers and Constitutional Isomers 165

4.1Isomerism: A Relationship 165

4.2Conformers: Rotational Conformations, Newman Projections, and
Dihedral Angles 166
4.3Conformers: Energy Changes and Conformational Analysis 169
4.4Conformers: Cyclic Alkanes and Ring Strain 174
4.5Conformers: The Most Stable Conformations of Cyclohexane,
Cyclopentane, Cyclobutane, and Cyclopropane 178
4.6Conformers: Cyclopentane, Cyclohexane, Pseudorotation,
and Chair Flips 179
4.7Strategies for Success: Drawing Chair Conformations
of Cyclohexane 182
4.8Conformers: Monosubstituted Cyclohexanes 184
4.9Conformers: Disubstituted Cyclohexanes, Cis and Trans
Isomers, and Haworth Projections 188
4.10 Strategies for Success: Molecular Modeling Kits and
Chair Flips 189
4.11 Constitutional Isomerism: Identifying Constitutional
Isomers 190
4.12 Constitutional Isomers: Index of Hydrogen
Deficiency (Degree of Unsaturation) 193


4.13 Strategies for Success: Drawing All Constitutional Isomers of a Given
Formula 195

THE ORGANIC CHEMISTRY OF BIOMOLECULES
4.14 Constitutional Isomers and Biomolecules: Amino Acids and
Monosaccharides 198
4.15 Saturation and Unsaturation in Fats and Oils 199

Chapter Summary and Key Terms 201

Problems 202

5

Isomerism 2
Chirality, Enantiomers, and Diastereomers 208

5.1Defining Configurational Isomers, Enantiomers, and
Diastereomers 208
5.2Enantiomers, Mirror Images, and Superimposability 210
5.3Strategies for Success: Drawing Mirror Images 212
5.4Chirality 214
5.5Diastereomers 224
5.6Fischer Projections and Stereochemistry 229
5.7Strategies for Success: Converting between Fischer Projections and
Zigzag Conformations 231
5.8Physical and Chemical Properties of Isomers 234
5.9Stability of Double Bonds and Chemical Properties of Isomers 238
5.10 Separating Configurational Isomers 240
5.11 Optical Activity 241

THE ORGANIC CHEMISTRY OF BIOMOLECULES
5.12 The Chirality of Biomolecules 245
5.13 The d/l System for Classifying Monosaccharides and
Amino Acids 247
5.14 The d Family of Aldoses 248

Chapter Summary and Key Terms 250

Problems 251
INTERCHAPTER

C

Stereochemistry in Nomenclature
R and S Configurations about Asymmetric Carbons
and Z and E Configurations about Double Bonds 258

C.1Priority of Substituents and Stereochemical Configurations at
Asymmetric Carbons: R/S Designations 258
C.2Stereochemical Configurations of Alkenes: Z/E Designations 268

Problems 272

x   Contents


6

The Proton Transfer Reaction
An Introduction to Mechanisms, Thermodynamics, and
Charge Stability 274

6.1An Introduction to Reaction Mechanisms: The Proton Transfer Reaction
and Curved Arrow Notation 275
6.2Chemical Equilibrium and the Equilibrium Constant, Keq 277
6.3Thermodynamics and Gibbs Free Energy 287
6.4Strategies for Success: Functional Groups and Acidity 289
6.5Relative Strengths of Charged and Uncharged Acids: The Reactivity of

Charged Species 291
6.6Relative Acidities of Protons on Atoms with Like Charges 293
6.7Strategies for Success: Ranking Acid and Base Strengths — ​The
Relative Importance of Effects on Charge 308
6.8Strategies for Success: Determining Relative Contributions by
Resonance Structures 312

THE ORGANIC CHEMISTRY OF BIOMOLECULES
6.9The Structure of Amino Acids in Solution as a Function of pH 314
6.10 Electrophoresis and Isoelectric Focusing 317

Chapter Summary and Key Terms 320

Problems 321

7

An Overview of the Most Common
Elementary Steps 328

7.1Mechanisms as Predictive Tools: The Proton Transfer Step
Revisited 329
7.2Bimolecular Nucleophilic Substitution (SN2) Steps 334
7.3Bond-Forming (Coordination) and Bond-Breaking (Heterolysis)
Steps 337
7.4Nucleophilic Addition and Nucleophile Elimination Steps 339
7.5Bimolecular Elimination (E2) Steps 341
7.6Electrophilic Addition and Electrophile Elimination Steps 343
7.7Carbocation Rearrangements: 1,2-Hydride Shifts and 1,2-Alkyl
Shifts 345

7.8The Driving Force for Chemical Reactions 347
7.9Keto–Enol Tautomerization: An Example of Bond Energies as the Major
Driving Force 350

Chapter Summary and Key Terms 355

Problems 356


INTERCHAPTER

D

Molecular Orbital Theory,
Hyperconjugation, and Chemical
Reactions 364

D.1Relative Stabilities of Carbocations and Alkenes: Hyperconjugation 364
D.2MO Theory and Chemical Reactions 366

Problems 376
INTERCHAPTER

E

Naming Compounds with a Functional
Group That Calls for a Suffix 1
Alcohols, Amines, Ketones, and Aldehydes 377

E.1The Basic System for Naming Compounds Having a Functional Group

That Calls for a Suffix: Alcohols and Amines 378
E.2Naming Ketones and Aldehydes 384
E.3Trivial Names of Alcohols, Amines, Ketones, and Aldehydes 386

Problems 390

8

An Introduction to Multistep Mechanisms
SN1 and E1 Reactions and Their Comparisons to SN2
and E2 Reactions 393

8.1The Unimolecular Nucleophilic Substitution (SN1) Reaction 394
8.2The Unimolecular Elimination (E1) Reaction 398
8.3Direct Experimental Evidence for Reaction Mechanisms 400
8.4The Kinetics of SN2, SN1, E2, and E1 Reactions 400
8.5Stereochemistry of Nucleophilic Substitution and Elimination
Reactions 406
8.6The Reasonableness of a Mechanism: Proton Transfers and
Carbocation Rearrangements 421
8.7Resonance-Delocalized Intermediates in Mechanisms 432

Chapter Summary and Key Terms 434

Problems 434

9

Nucleophilic Substitution and Elimination
Reactions 1

Competition among SN2, SN1, E2, and E1
Reactions 442

9.1The Competition among SN2, SN1, E2, and E1 Reactions 443
9.2Rate-Determining Steps Revisited: Simplified Pictures of the SN2, SN1,
E2, and E1 Reactions 445
xii   Contents


9.3Factor 1: Strength of the Attacking Species 447
9.4Factor 2: Concentration of the Attacking Species 456
9.5Factor 3: Leaving Group Ability 458
9.6Factor 4: Type of Carbon Bonded to the Leaving Group 464
9.7Factor 5: Solvent Effects 470
9.8Factor 6: Heat 476
9.9Predicting the Outcome of an SN2/SN1/E2/E1 Competition 477
9.10 Regioselectivity in Elimination Reactions: Zaitsev’s Rule 482
9.11 Intermolecular Reactions versus Intramolecular Cyclizations 485
9.12 Kinetic Control, Thermodynamic Control, and Reversibility 487

THE ORGANIC CHEMISTRY OF BIOMOLECULES
9.13 Nucleophilic Substitution Reactions and Monosaccharides: The
Formation and Hydrolysis of Glycosides 490

Chapter Summary and Key Terms 493

Reaction Tables 494

Problems 495
INTERCHAPTER

F

Naming Compounds with a Functional
Group That Calls for a Suffix 2
Carboxylic Acids and Their Derivatives 503

F.1Naming Carboxylic Acids, Acid Chlorides, Amides, and Nitriles 503
F.2Naming Esters and Acid Anhydrides 507
F.3Trivial Names of Carboxylic Acids and Their Derivatives 510

Problems 513

10

Nucleophilic Substitution and
Elimination Reactions 2
Reactions That Are Useful for Synthesis 515

10.1
Nucleophilic Substitution: Converting Alcohols into Alkyl Halides
Using PBr3 and PCl3 516
10.2
Nucleophilic Substitution: Alkylation of Ammonia and Amines 520
10.3
Nucleophilic Substitution: Alkylation of α Carbons 523
10.4
Nucleophilic Substitution: Halogenation of α Carbons 528
10.5
Nucleophilic Substitution: Diazomethane Formation of Methyl

Esters 533
10.6
Nucleophilic Substitution: Formation of Ethers and Epoxides 535
10.7
Nucleophilic Substitution: Epoxides and Oxetanes as Substrates 540
10.8
Elimination: Generating Alkynes via Elimination Reactions 548

Contents   xiii


10.9
Elimination: Hofmann Elimination 551

Chapter Summary and Key Terms 554

Reaction Tables 555

Problems 557

11

Electrophilic Addition to Nonpolar
π Bonds 1
Addition of a Brønsted Acid 563

11.1
The General Electrophilic Addition Mechanism: Addition of a Strong
Brønsted Acid to an Alkene 565
11.2

Benzene Rings Do Not Readily Undergo Electrophilic Addition of
Brønsted Acids 568
11.3
Regiochemistry: Production of the More Stable Carbocation and
Markovnikov’s Rule 569
11.4
Carbocation Rearrangements 573
11.5
Stereochemistry 574
11.6
Addition of a Weak Acid: Acid Catalysis 576
11.7
Electrophilic Addition of a Strong Brønsted Acid to an Alkyne 578
11.8
Acid-Catalyzed Hydration of an Alkyne: Synthesis of a Ketone 581
11.9
Electrophilic Addition of a Brønsted Acid to a Conjugated Diene:
1,2-Addition and 1,4-Addition 583
11.10Kinetic versus Thermodynamic Control in Electrophilic Addition to a
Conjugated Diene 586

THE ORGANIC CHEMISTRY OF BIOMOLECULES
11.11Terpene Biosynthesis: Carbocation Chemistry in Nature 589

Chapter Summary and Key Terms 594

Reaction Table 595

Problems 596

12

Electrophilic Addition to Nonpolar
π Bonds 2
Reactions Involving Cyclic Transition States 601

12.1
Electrophilic Addition via a Three-Membered Ring: The General
Mechanism 602
12.2
Electrophilic Addition of Carbenes: Formation of Cyclopropane
Rings 604
12.3
Electrophilic Addition Involving Molecular Halogens: Synthesis of
1,2-Dihalides and Halohydrins 607
12.4
Oxymercuration–Reduction: Addition of Water 614
12.5
Epoxide Formation Using Peroxyacids 620
12.6
Hydroboration–Oxidation: Anti-Markovnikov Syn Addition of Water to
an Alkene 623
xiv   Contents


12.7
Hydroboration–Oxidation of Alkynes 631

Chapter Summary and Key Terms 632

Reaction Tables 633

Problems 635

13

Organic Synthesis 1
Beginning Concepts in Designing Multistep
Synthesis 641

13.1
Writing the Reactions of an Organic Synthesis 642
13.2
Cataloging Reactions: Functional Group Transformations and
Carbon–Carbon Bond-Forming/Brucleic
acid. The cyclic sugar must be deoxyribose, in which the ribose oxygen indicated is not
present. The nitrogenous base shown is cytosine, but could also be adenine, guanine, or
thymine.
1.14 An Introduction to Proteins, Carbohydrates, and Nucleic Acids: Fundamental Building Blocks and Functional Groups   43


These four bases are found in RNA.
These four bases are found in DNA.

O
NH
N
H

N

O

Uracil
(U)

N
H

NH2

NH2

O
N

NH

N
H

NH2

N
Guanine
(G)

O
N

N

N
H

N
Adenine
(A)

NH
N
H

O

Cytosine
(C)

O

Thymine
(T)

FIGURE 1-40  ​
Nitrogenous bases ​The identity of a nucleotide is specified by the
nitrogenous base bonded to the sugar ring. U, G, A, and C are found in RNA, whereas G, A, C,
and T are found in DNA. In a nucleotide, carbon 19 of the ribose sugar unit connects to the
highlighted nitrogen atom.

nitrogenous bases that appear in RNA: uracil, guanine, adenine, and cytosine (abbreviated U, G, A, and C, respectively; Fig. 1-40). There are four types of nitrogenous bases
that appear in DNA, too: G, A, C, and thymine (T). Thus, three of the bases in DNA
are the same as the bases in RNA. Only T (in DNA) is different from U (in RNA).

Notice the functional groups in these nitrogenous bases. An O w C i N group,
for example, which is characteristic of an amide, appears in guanine, and a C w C
bond, which characterizes an alkene, appears in uracil and thymine. (In Chapter 14,
we learn that this C w C bond is better classified as being part of an aromatic ring
rather than an alkene.)

Your Turn 1.17

Circle and label the functional groups mentioned above that appear in U, G, A,
C, and T in Figure 1-40.

In subsequent units on biomolecules, we examine some of the details of the chemical processes involving DNA and RNA. In Section 14.11, for example, we examine
the complementarity among the nitrogenous bases.
problem 1.37  ​For each of the following nucleotides, (a) circle and label the
phosphate group, the sugar group, and the nitrogenous base; (b) Determine whether
it can be part of RNA or DNA; and (c) identify the nitrogenous base that it contains.
O

NH2
N
O

P

O

–

N

O
H

O

N

P

O

–

H
H

N

O
H

(i)

44  CHAPTER 1  Atomic and Molecular Structure

O

H

H

O

NH

N

O

H

H

H
O

H
(ii)

O


Chapter Summary and Key Terms

Organic chemistry is the subdiscipline of chemistry in
which the focus is on compounds containing carbon atoms.

●

(Section 1.1; Objective 1)

Carbon’s ability to form four strong covalent bonds is what
gives rise to the great variety of organic compounds known.

●

(Section 1.2; Objective 2)

No more than two electrons can occupy an atom’s first shell.
As many as eight electrons can occupy an atom’s second shell.
A second or higher level shell containing eight electrons (an
octet) is especially stable (the octet rule). (Section 1.3b;

●


Formal charge represents a particular way in which valence
electrons are assigned to individual atoms within a molecule.
To determine formal charges, each pair of electrons in a
covalent bond is split evenly between the two atoms bonded
together. (Section 1.9; Objective 8)

●

Resonance exists when two or more valid Lewis structures can
be drawn for a given molecular species. (Section 1.10)

●

Each Lewis structure is imaginary and is called a resonance structure. (Objective 9)
● The properties of the one, true species — ​the resonance

hybrid — represent a weighted average of all the resonance
structures. (Objective 10)
● The greater the stability of a given resonance structure,
the greater its contribution to the resonance hybrid.
●

Objective 3)

An atom’s ground state (i.e., lowest energy) electron configuration is derived using the following three rules. (Section 1.3c;

●

Objective 4)

Pauli’s exclusion principle: Up to two electrons, opposite
in spin, may occupy an orbital.
●The aufbau principle: Electrons occupy the lowest energy
orbitals available.
● Hund’s rule: If orbitals have the same energy, then each
orbital is singly occupied before a second electron fills it.
●

Sharing of a pair of electrons by two atoms lowers the energy
of the system, creating a covalent bond. Some atoms can
share two or three pairs of electrons, creating double or triple
bonds, respectively. Double bonds are shorter and stronger
than single bonds, and triple bonds are shorter and stronger
than double bonds. (Section 1.4; Objective 5)

●


Lewis structures illustrate a molecule’s connectivity. They
account for all valence electrons, differentiating between
bonding pairs and lone pairs of electrons. They indicate,
moreover, which atoms are bonded together and by what
types of bonds. Lewis structures are constructed so that the
maximum number of atoms have filled valence shells (i.e.,
duets or octets). (Section 1.5; Objective 6)

(Objective 9)

Resonance structures are related by hypothetically shifting
around lone pairs of electrons, and pairs of electrons from
double and triple bonds. The atoms in the molecule must
remain frozen in place. (Section 1.11; Objective 10)

●

Shorthand notation is used throughout organic chemistry to
draw molecules more quickly and efficiently. Lone pairs are
often omitted. (Section 1.12; Objective 11)

●

Condensed formulas are used primarily to write a molecule in a line of text, with hydrogens written adjacent to
the atom to which they are bonded.
● Line structures show all bonds explicitly, except bonds to
hydrogen. Hydrogen atoms are omitted if they are bonded
to carbon. Carbon atoms are not drawn explicitly, but are

assumed to reside at the intersection of two lines and at the
end of a line (unless otherwise indicated).
●

●

The electrons in a nonpolar covalent bond are shared equally.
Polar covalent bonds arise when atoms with moderate differences in electronegativity are bonded together. Ionic bonds
arise when there are large differences in electronegativity. (Sec-

●


Functional groups are common bonding arrangements of
relatively few atoms. Functional groups dictate the behavior
of entire molecules — ​that is, molecules with the same
functional groups tend to behave similarly. (Section 1.13;

●

Objective 12)

tions 1.7 and 1.8; Objective 7)

Problems
1.3  ​Atomic Structure and Ground State Electron Configurations
1.38 In which of the following orbitals does an electron possess the most energy? 2s; 3s; 4s; 3p; 2p
1.39 For each pair, identify the orbital in which an electron possesses more energy. (a) 4s or 5s; (b) 5p or 5d
1.40 Write the ground state electron configuration of each of the following atoms. For each atom, identify the valence electrons
and the core electrons. (a) Al; (b) S; (c) O; (d) N; (e) F

Problems  45


1.4  ​The Covalent Bond: Bond Energy and Bond Length
1.41 Consider a molecule of N2. For each pair of distances between the two N atoms, determine which distance represents a
higher energy. Explain. (a) 50 pm or 75 pm; (b) 75 pm or 110 pm; (c) 110 pm or 150 pm; (d) 150 pm or 160 pm
1.42 In which of the following molecules is the bond between carbon and nitrogen the shortest? In which molecule is it the
strongest? H i C { N; H2C w NH; H3C i NH2
1.43 According to Table 1-2, which of the following compounds has the strongest single bond? The weakest? HCl; CH4; H2O; HF; Cl2

1.5–1.8  ​Lewis Dot Structures, Polarity, and Ionic Bonds
1.44 Draw Lewis structures for each of the following molecules: (a) CH5N (contains a bond between C and N); (b) CH3NO2
(contains a bond between C and N but no bonds between C and O); (c) CH2O; (d) CH2Cl2; (e) BrCN
1.45 For each structure below, determine whether it is a legitimate Lewis structure. If it is not, explain why not.
(a)

O

(b)

H

H
C

C

C

H

H

H

C

S
H H

(c)

H
C

H

H

H

O

C

C

(d)

O

O

N

N

H

(e)

H

H

C

N

H

H

H
+

H

C

H

1.46 Complete the Lewis structure for each of the following molecules using the information provided in Table 1-4. You may
assume that all formal charges are zero. All H atoms are shown; add only bonding pairs and lone pairs of electrons.
(a)

H
N
H

O

C
O

C
F

C

C

(b)

H
H
C

C

N

(c)

H

H

H
H

C
C

C

C

C

C
C

H

H

H

C

C

H

H

C

N

O

H

H

H

1.47 Rank the following in order of increasing negative charge on carbon. CH3 i CH3; CH3 i MgBr; CH3 i Li; CH3 i F;
CH3 i OH; CH3 i NH2
1.48 Which of the following contains an ionic bond? (a) H2; (b) NaCl; (c) NaOH; (d) CH3ONa; (e) CH4; (f) HOCH2CH3;
(g) LiNHCH3; (h) CH3CH2CO2K; (i) C6H5NH3Cl

1.9  ​Assigning Electrons to Atoms in Molecules: Formal Charge
1.49 In the methoxide anion (CH3O2), is it possible for a double bond to exist between C and O, given that the negative charge
resides on O? Explain why or why not.
1.50 Draw Lewis structures for each of the following ions. One atom in each ion has a formal charge that is not zero.
Determine which atom it is, and what the formal charge is. (a) the C2H5 anion; (b) the CH3O cation; (c) the CH6N cation;
(d) the CH5O cation; (e) the C3H3 anion (all three H atoms are on the same carbon)

1.51 Identify the formal charge on each atom in the following
species. Assume that all valence electrons are shown.

H
H

H

N
H

C

C
C

H
H

N

46  CHAPTER 1  Atomic and Molecular Structure

H
C

C

O
C

C

N

H

C
O

C
F


1.52 The structure at the right is a skeleton of an anion having the overall formula C6H6NO2. The hydrogen
O
C C
atoms are not shown.
C C
C
(a)Draw a complete Lewis structure in which the 21 formal charge is on N. Include all H atoms and
C
N
valence electrons.
(b)Do the same for a Lewis structure with the 21 formal charge on O.
(c)Do the same for a Lewis structure with the 21 formal charge on the C atom that is bonded to three other C atoms.

1.10 and 1.11  ​Resonance Theory; Drawing All Resonance Structures
1.53 Draw all resonance contributors for each of the following molecules or ions. Be sure to include the curved arrows that
indicate which pairs of electrons are shifted in going from one resonance structure to the next.

(a)CH3NO2
(b)CH3CO2
2
(c)CH3CHCHCH2
i C single bonds)
2 (the ion has two C 
(d)C5H5N (a ring is formed by the C and N atoms, and each H is bonded to C)
(e)C4H5N (a ring is formed by the C and N atoms, the N is bonded to one H, and each C is bonded to one H)
1.54 Draw the resonance hybrid of CH3NO2 in Problem 1.53(a).
1.55 (a) Draw all resonance contributors of sulfuric acid, H2SO4 (the S atom is bonded to four O atoms). (b) Which resonance
structure contributes the most to the resonance hybrid? (c) Which resonance structure contributes the least to the
resonance hybrid?
1.56 Experiments indicate that the carbon–carbon bonds in
cyclobutadiene are of two different lengths. Argue whether
or not cyclobutadiene has a resonance structure.

132 pm
160 pm

Cyclobutadiene

1.57 The two species shown are structurally very similar. Draw
all resonance structures for each species and determine
which is more stable. Explain.

(a)

(b)

+

+

O

O

1.58 The two species shown are structurally very similar. Draw
all resonance structures for each species and determine
which is more stable. Explain.

(a)

O

(b)

–

O

–

O
O

1.12  ​Shorthand Notations
1.59 Redraw the following structure of glucose as a line structure.

H

H

H

H

H

O

C

H

C
O
H

C

C

H

O

C

H

O
C

H
O

O

H

H
Glucose

Problems  47


1.60 Redraw the following line structure of sucrose as a
complete Lewis structure. Include all hydrogen atoms
and lone pairs.

OH
HO

OH

O

O

OH

O

HO

OH

OH HO
Sucrose

1.61 Draw the following Lewis structures using condensed formulas.
(a)

H

H

H

H

H

C

C

C

C

H

H

H

H

(b)

H

H

H

H

H

H

C

C

C

C

H

H

(c)

H

H

H

H
H

C

H
H

H

C

C

C

C

H
(d)

H

H
H
H

C
C
H

C
C

H
H
H

C
H

H

H

(e)

H

H

C

H

C
H

C

H

C

H

C

C
H

H

H

H

H

C
H

C

O

H

H
C

H

H

(f)

H

H

H

C

C

H

H

H

H

1.62 Draw the molecules in Problem 1.61 using line structures.
1.63 Draw Lewis structures for the following molecules. Include all lone pairs and H atoms.
(a)

OH

(b)

Cl Cl

(d)

O

(c)

O

O

(e)

N

O
(f)

+

(g)

–

(i)

(h)

O
+

H3N

O–

–

1.64 Draw each of the species in Problem 1.63 as a condensed formula.
1.65 Redraw the given line structure of cholesterol as a
condensed formula. What advantages do line structures
have?

HO

Cholesterol

48  CHAPTER 1  Atomic and Molecular Structure

H

H


1.13  ​An Overview of Organic Compounds: Functional Groups
1.66 Circle each functional group in glucose (Problem 1.59) and sucrose (Problem 1.60). What compound class is
characteristic of each of those functional groups?
1.67 Dimethyl sulfide contains a functional group that is not listed in Table 1-6. Which functional group in Table 1-6 do you
think its reactivity might resemble?
H3C i S i CH3
Dimethyl sulfide

1.68 Which one of the following compounds do you think will behave most similarly to ethanol (CH3CH2OH)? Explain.
O
C
H2O

CH3OCH3

CH3CO2H

A

B

C

H

H3C
D

1.69 Identify all functional groups that are present in
strychnine, a highly toxic alkaloid used as a pesticide
to kill rodents, whose line structure is shown here.
What compound class is characteristic of each of those
functional groups?

N

N
O

O
Strychnine

1.70 Identify all functional groups that are present in
doxorubicin, a drug used as an antibiotic and cancer
therapeutic, whose line structure is shown here. What
compound class is characteristic of each of those
functional groups?

O

OH

O

OH
OH

O

O

OH

O

O
OH

NH2
Doxorubicin

1.14  ​The Organic Chemistry of Biomolecules
1.71 The R group in alanine is –CH3, whereas the R group in aspartic acid is –CH2CO2H. After consulting Figure 1-34, draw the
complete Lewis structure for each of these amino acids.
1.72 Shown here is a tripeptide, which consists of three
amino acids linked together in a chain. Circle and name
each amino acid.

H
N

H2N
O

O

N
H
OH

OH

O

Problems  49