CONTENTS
Preface v
Chapter 1 | Atomic and Molecular Structure 1
Interchapter A | Nomenclature: The Basic System for Naming Simple Organic
Compounds— Alkanes, Haloalkanes, Nitroalkanes, Cycloalkanes,
and Ethers 35
Chapter 2 | Three- Dimensional Geometry, Intermolecular Interactions, and
Physical Properties 47
Chapter 3 | Orbital Interactions 1: Hybridization and Two- Center Molecular Orbitals 75
Interchapter B | Naming Alkenes, Alkynes, and Benzene Derivatives 103
Chapter 4 | Isomerism 1: Conformers and Constitutional Isomers 114
Chapter 5 | Isomerism 2: Chirality, Enantiomers, and Diastereomers 143
Interchapter C | Stereochemistry in Nomenclature: R and S Configurations about
Asymmetric Carbons and Z and E Configurations about Double Bonds 172
Chapter 6 | The Proton Transfer Reaction: An Introduction to Mechanisms,
Thermodynamics, and Charge Stability 184
Chapter 7 | An Overview of the Most Common Elementary Steps 211
Interchapter D | Molecular Orbital Theory, Hyperconjugation, and Chemical Reactions 243
Interchapter E | Naming Compounds with a Functional Group That Calls for a
Suffix 1: Alcohols, Amines, Ketones, and Aldehydes 254
Chapter 8 | An Introduction to Multistep Mechanisms: SN
1 and E1 Reactions and
Their Comparisons to SN
2 and E2 Reactions 265
Chapter 9 | Nucleophilic Substitution and Elimination Reactions 1: Competition
among SN
2, SN
1, E2, and E1 Reactions 292
Interchapter F | Naming Compounds with a Functional Group That Calls for a
Suffix 2: Carboxylic Acids and Their Derivatives 320
Chapter 10 | Nucleophilic Substitution and Elimination Reactions 2: Reactions
That Are Useful for Synthesis 331
Chapter 11 | Electrophilic Addition to Nonpolar π Bonds 1: Addition of a Brønsted
Acid 361
Chapter 12 | Electrophilic Addition to Nonpolar π Bonds 2: Reactions Involving
Cyclic Transition States 388
Chapter 13 | Organic Synthesis 1: Beginning Concepts in Designing Multistep Synthesis 415
Chapter 14 | Orbital Interactions 2: Extended π Systems, Conjugation, and Aromaticity 445
Chapter 15 | Structure Determination 1: Ultraviolet– Vis i ble and Infrared Spectroscopies 469
Chapter 16 | Structure Determination 2: Nuclear Magnetic Resonance Spectroscopy
and Mass Spectrometry 500
Chapter 17 | Nucleophilic Addition to Polar π Bonds 1: Addition of Strong Nucleophiles 533
Chapter 18 | Nucleophilic Addition to Polar π Bonds 2: Weak Nucleophiles and Acid
and Base Catalysis 567
Chapter 19 | Organic Synthesis 2: Intermediate Topics in Synthesis Design, and
Useful Redox and Carbon– Carbon Bond- Forming Reactions 606
Chapter 20 | Nucleophilic Addition– Elimination Reactions 1: The General
Mechanism Involving Strong Nucleophiles 645
Chapter 21 | Nucleophilic Addition– Elimination Reactions 2: Weak Nucleophiles 681
Chapter 22 | Aromatic Substitution 1: Electrophilic Aromatic Substitution on
Benzene; Useful Accompanying Reactions 723
Chapter 23 | Aromatic Substitution 2: Reactions of Substituted Benzenes and Other Rings 752
Chapter 24 | The Diels– Alder Reaction and Other Pericyclic Reactions 790
Chapter 25 | Reactions Involving Free Radicals 826
Interchapter G | Fragmentation Pathways in Mass Spectrometry 856
Chapter 26 | Polymers 876
Credits 902
iv • CONTENTS
1 • Chapter 1
LearNING OBJeCtIVeS
Determine the number of valence and/or core electrons for an atom or ion.
Interpret the electron configuration and formal charge for an atom or ion.
Identify forces that are involved in chemical bonding.
Analyze an energy versus internuclear distance diagram to understand the properties of a chemical bond.
Predict the properties of a covalent bond based on known periodic trends, and vice versa.
Assess the validity of a Lewis structure.
Apply knowledge of chemical structure to determine the formal charge of an unknown species.
Compare a series of structures to determine if they are resonance structures.
Determine the molecular formula of an organic compound from a structural drawing or condensed formula.
Master the structural drawing of organic molecules— specifically, Lewis structures and line structures.
Assimilate your knowledge of molecular structure to identify and/or draw organic functional groups.
Identify the key structural features of amino acids, saccharides, and nucleotides.
Deduce and draw the resonance structures that contribute to the resonance hybrid, and vice versa.
Elaborate how an electrostatic potential map correlates to molecular structure and properties.
Predict the ionic or covalent nature of an organic structure from physical property data.
Indicate bond dipoles and lone pairs on an organic structure, and predict how these structural features impact chemical reactivity.
Apply the concept of resonance to predict the outcome of a chemical reaction.
Depict electron delocalization via resonance using appropriate arrow notation.
Recognize and name functional groups within a complex molecule.
Draw a structure of a given molecular formula that contains a specific functional group.
Chapter 1: atomic and Molecular Structure
2 • Chapter 1
1
MULTIPLE CHOICE
- Which orbital does NOT house core electrons for a bromine atom?
a. 1s d. 2s
b. 4p e. 3s
c. 3p
ANS: B DIF: Easy REF: 1.3
OBJ: Determine the number of valence and/or core electrons for an atom or ion.
MSC: Remembering - An atom of which element would have an electron configuration of 1s
22s
22p
63s
23p
1?
a. Al d. Si
b. Ne e. Na
c. B
ANS: A DIF: Easy REF: 1.3
OBJ: Interpret the electron configuration and formal charge for an atom or ion.
MSC: Understanding - Which electron configuration is correct for a carbon atom with a formal charge of −1?
a. 1s
22s
22p
63s
1 d. 1s
22s
22p
63s
23p
5
b. 1s
22s
22p
3 e. 1s
22s
22p
4
c. 1s
22s
22p
5
ANS: B DIF: Easy REF: 1.3 | 1.9
OBJ: Interpret the electron configuration and formal charge for an atom or ion.
MSC: Understanding - Which electron configuration is correct for the carbon of a carbocation?
a. 1s
22s
22p
1 d. 1s
22s
22p
63s
23p
5
b. 1s
22s
22p
3 e. 1s
22s
22p
4
c. 1s
22s
22p
5
ANS: A DIF: Easy REF: 1.3 | 1.9
OBJ: Interpret the electron configuration and formal charge for an atom or ion.
MSC: Understanding - Which electron configuration is correct for a Ca2+ ion?
a. 1s
22s
22p
63s
23p
1 d. 1s
22s
22p
63s
23p
64s
24p
6
b. 1s
22s
22p
63s
23p
64s
2 e. 1s
22s
22p
63s
2
c. 1s
22s
22p
63s
23p
6
ANS: C DIF: Easy REF: 1.3 | 1.9
OBJ: Interpret the electron configuration and formal charge for an atom or ion.
MSC: Applying