Fundamentals of Organic Chemistry

by McMurry, John E.

• ISBN13: 9780534395735
• ISBN10: 0534395732
• Edition: 5th
• Format: Hardcover
• Copyright: 2002-07-15
• Publisher: Brooks Cole

Summary

Written for the short course-where content must be thorough, but to-the-point, FUNDAMENTALS OF ORGANIC CHEMISTRY, Fifth Edition provides an effective, clear, and readable introduction to the beauty and logic of organic chemistry. McMurry presents only those subjects needed for a brief course while maintaining the important pedagogical tools commonly found in larger books. With clear explanations, thought-provoking examples, and an innovative vertical format for explaining reaction mechanisms, FUNDAMENTALS takes a modern approach: primary organization is by functional group, beginning with the simple (alkanes) and progressing to the more complex. Within the primary organization, there is also an emphasis on explaining the fundamental mechanistic similarities of reactions. Through this approach, memorization is minimized and understanding is maximized. This new edition represents a major revision. The text has been revised at the sentence level to further improve clarity and readability; many new examples and topics of biological relevance have been added; and many new features have been introduced.

Table of Contents

Preface	xvi
A Note for Students	xxi
Structure and Bonding; Acids and Bases	1	(33)
Atomic Structure	3	(2)
Electron Configuration of Atoms	5	(1)
Development of Chemical Bonding Theory	6	(1)
The Nature of Chemical Bonds	7	(3)
Forming Covalent Bonds: Valence Bond Theory	10	(1)
Hybridization: sp3 Orbitals and the Structure of Methane	11	(1)
Hybridization: sp3 Orbitals and the Structure of Ethane	12	(1)
Hybridization: sp2 Orbitals and the Structure of Ethylene	13	(3)
Hybridization: sp Orbitals and the Structure of Acetylene	16	(1)
Polar Covalent Bonds: Electronegativity	17	(3)
Acids and Bases: The Brønsted--Lowry Definition	20	(4)
Acids and Bases: The Lewis Definition	24	(10)
Interlude Chemicals, Toxicity, and Risk	26	(1)
Summary and Key Words	27	(1)
Working Problems	28	(1)
Visualizing Chemistry / Additional Problems	29	(5)
The Nature of Organic Compounds: Alkanes	34	(40)
Functional Groups	35	(6)
Alkanes and Alkyl Groups: Isomers	41	(5)
Naming Branched-Chain Alkanes	46	(3)
Properties of Alkanes	49	(1)
Conformations of Ethane	50	(3)
Drawing Chemical Structures	53	(1)
Cycloalkanes	54	(1)
Cis-Trans Isomerism in Cycloalkanes	55	(2)
Conformations of Some Cycloalkanes	57	(3)
Axial and Equatorial Bonds in Cyclohexane	60	(1)
Conformational Mobility of Cyclohexane	61	(13)
Interlude Gasoline	64	(2)
Summary and Key Words	66	(1)
Visualizing Chemistry / Additional Problems	67	(7)
The Nature of Organic Reactions: Alkenes	74	(31)
Naming Alkenes	75	(3)
Electronic Structure of Alkenes	78	(1)
Cis--Trans Isomers of Alkenes	79	(2)
Sequence Rules: The E,Z Designation	81	(3)
Kinds of Organic Reactions	84	(2)
How Reactions Occur: Mechanisms	86	(3)
The Mechanism of an Organic Reaction: Addition of HCI to Ethylene	89	(3)
Describing a Reaction: Reaction Energy Diagrams and Transition States	92	(2)
Describing a Reaction: Intermediates	94	(11)
Interlude Terpenes: Naturally Occurring Alkenes	96	(2)
Summary and Key Words	98	(1)
Visualizing Chemistry / Additional Problems	99	(6)
Reactions of Alkenes and Alkynes	105	(38)
Addition of HX to Alkenes: Hydrohalogenation	106	(1)
Orientation of Alkene Addition Reactions: Markovnikov's Rule	106	(3)
Carbocation Structure and Stability	109	(2)
Addition of H2O to Alkenes: Hydration	111	(2)
Addition of X2 to Alkenes: Halogenation	113	(2)
Addition of H2 to Alkenes: Hydrogenation	115	(1)
Oxidation of Alkenes: Hydroxylation and Cleavage	116	(2)
Biological Addition Reactions of Alkenes	118	(1)
Addition of Radicals to Alkenes: Polymers	119	(3)
Conjugated Dienes	122	(2)
Stability of Allylic Carbocations: Resonance	124	(2)
Drawing and Interpreting Resonance Forms	126	(2)
Alkynes and Their Reactions	128	(15)
Interlude Natural Rubber	133	(1)
Summary and Key Words	134	(1)
Summary of Reactions / Visualizing Chemistry / Additional Problems	135	(8)
Aromatic Compounds	143	(34)
Structure of Benzene: The Kekule Proposal	144	(1)
Structure of Benzene: The Resonance Proposal	145	(1)
Naming Aromatic Compounds	146	(3)
Electrophilic Aromatic Substitution Reactions: Bromination	149	(4)
Other Electrophilic Aromatic Substitution Reactions	153	(1)
The Friedel-Crafts Alkylation and Acylation Reactions	154	(2)
Substituent Effects in Electrophilic Aromatic Substitution	156	(2)
An Explanation of Substituent Effects	158	(4)
Oxidation and Reduction of Aromatic Compounds	162	(1)
Polycyclic Aromatic Hydrocarbons	163	(1)
Organic Synthesis	164	(13)
Interlude Aspirin, NSAIDs, and COX-2 Inhibitors	167	(2)
Summary and Key Words	169	(1)
Summary of Reactions / Visualizing Chemistry / Additional Problems	170	(7)
Stereochemistry	177	(34)
Stereochemistry and the Tetrahedral Carbon	178	(2)
The Reason for Handedness in Molecules: Chirality	180	(3)
Optical Activity	183	(1)
Specific Rotation	184	(2)
Pasteur's Discovery of Enantiomers	186	(1)
Sequence Rules for Specifying Configuration	187	(4)
Diastereomers	191	(2)
Meso Compounds	193	(2)
Molecules with More Than Two Stereocenters	195	(1)
Racemic Mixtures and the Resolution of Enantiomers	196	(3)
Physical Properties of Stereoisomers	199	(1)
A Brief Review of Isomerism	199	(2)
Chirality in Nature	201	(10)
Interlude Chiral Drugs	203	(1)
Summary and Key Words	204	(1)
Visualizing Chemistry / Additional Problems	205	(6)
Alkyl Halides	211	(32)
Naming Alkyl Halides	212	(1)
Preparing Alkyl Halides	213	(2)
Reactions of Alkyl Halides: Grignard Reagents	215	(2)
Nucleophilic Substitution Reactions	217	(3)
The SN2 Reaction	220	(4)
The SN1 Reaction	224	(4)
Eliminations: The E2 Reaction	228	(2)
Eliminations: The E1 Reaction	230	(2)
A Summary of Reactivity: SN1, S2, E1, E2	232	(1)
Substitution Reactions in Living Organisms	233	(10)
Interlude Naturally Occurring Organohalogen Compounds	234	(1)
Summary and Key Words	235	(1)
Summary of Reactions / Visualizing Chemistry / Additional Problems	235	(8)
Alcohols, Phenols, and Ethers	243	(33)
Naming Alcohols, Phenols, and Ethers	244	(2)
Properties of Alcohols, Phenols, and Ethers: Hydrogen Bonding	246	(2)
Properties of Alcohols and Phenols: Acidity	248	(2)
Synthesis of Alcohols	250	(3)
Reactions of Alcohols	253	(5)
Synthesis and Reactions of Phenols	258	(3)
Synthesis and Reactions of Ethers	261	(1)
Cyclic Ethers: Epoxides	262	(2)
Thiols and Sulfides	264	(12)
Interlude Ethyl Alcohol: Chemical, Drug, and Poison	266	(1)
Summary and Key Words	267	(1)
Summary of Reactions / Visualizing Chemistry / Additional Problems	268	(8)
Aldehydes and Ketones: Nucleophilic Addition Reactions	276	(29)
The Nature of Carbonyl Compounds	277	(2)
Naming Aldehydes and Ketones	279	(2)
Synthesis of Aldehydes and Ketones	281	(1)
Oxidation of Aldehydes	282	(1)
Nucleophilic Addition Reactions of Aldehydes and Ketones: Reduction	283	(2)
Nucleophilic Addition of Water: Hydration	285	(3)
Nucleophilic Addition of Alcohols: Acetal Formation	288	(2)
Nucleophilic Addition of Amines: Imine Formation	290	(1)
Nucleophilic Addition of Grignard Reagents: Alcohol Formation	291	(3)
Conjugate Nucleophilic Addition Reactions	294	(1)
Some Biological Nucleophilic Addition Reactions	295	(10)
Interlude Carbonyl Compounds for Insect Control	297	(1)
Summary and Key Words	298	(1)
Summary of Reactions / Visualizing Chemistry / Additional Problems	298	(7)
Carboxylic Acids and Derivatives	305	(42)
Naming Carboxylic Acids and Derivatives	306	(4)
Occurrence and Properties of Carboxylic Acids	310	(3)
Synthesis of Carboxylic Acids	313	(1)
Nucleophilic Acyl Substitution Reactions	314	(3)
Reactions of Carboxylic Acids	317	(3)
Chemistry of Acid Halides	320	(2)
Chemistry of Acid Anhydrides	322	(2)
Chemistry of Esters	324	(5)
Chemistry of Amides	329	(2)
Chemistry of Nitriles	331	(3)
Polymers from Carbonyl Compounds: Nylons and Polyesters	334	(13)
Interlude Vitamin C	336	(2)
Summary and Key Words	338	(1)
Summary of Reactions / Visualizing Chemistry / Additional Problems	338	(9)
Carbonyl Alpha-Substitution Reactions and Condensation Reactions	347	(32)
Keto--Enol Tautomerism	348	(4)
Reactivity of Enols: The Mechanism of Alpha-Substitution Reactions	352	(1)
Alpha Halogenation of Aldehydes and Ketones	353	(2)
Acidity of Alpha Hydrogen Atoms: Enolate Ion Formation	355	(3)
Reactivity of Enolate Ions	358	(1)
Alkylation of Enolate Ions	359	(3)
Carbonyl Condensation Reactions	362	(1)
Condensations of Aldehydes and Ketones: The Aldol Reaction	362	(2)
Dehydration of Aldol Products: Synthesis of Enones	364	(2)
Condensations of Esters: The Claisen Condensation Reaction	366	(2)
Biological Carbonyl Reactions	368	(11)
Interlude β-Lactam Antibiotics	370	(1)
Summary and Key Words	371	(1)
Summary of Reactions / Visualizing Chemistry / Additional Problems	372	(7)
Amines	379	(27)
Naming Amines	380	(3)
Structure and Properties of Amines	383	(1)
Basicity of Amines	383	(3)
Synthesis of Amines	386	(6)
Reactions of Amines	392	(1)
Heterocyclic Amines	393	(4)
Alkaloids: Naturally Occurring Amines	397	(9)
Interlude Opium and Opiates	398	(1)
Summary and Key Words	399	(1)
Summary of Reactions / Visualizing Chemistry / Additional Problems	400	(6)
Structure Determination	406	(35)
Infrared Spectroscopy and the Electromagnetic Spectrum	407	(3)
Infrared Spectroscopy of Organic Molecules	410	(5)
Ultraviolet Spectroscopy	415	(1)
Interpreting Ultraviolet Spectra: The Effect of Conjugation	416	(2)
Nuclear Magnetic Resonance Spectroscopy	418	(1)
The Nature of NMR Absorptions	419	(3)
Chemical Shifts	422	(1)
Chemical Shifts in 1H NMR Spectra	423	(2)
Integration of 1H NMR Spectra: Proton Counting	425	(1)
Spin--Spin Splitting in 1H NMR Spectra	426	(4)
Uses of 1H NMR Spectra	430	(1)
13C NMR Spectroscopy	430	(11)
Interlude Magnetic Resonance Imaging (MRI)	433	(1)
Summary and Key Words	434	(1)
Visualizing Chemistry / Additional Problems	435	(6)
Biomolecules: Carbohydrates	441	(31)
Classification of Carbohydrates	442	(2)
Configurations of Monosaccharides: Fischer Projections	444	(2)
D,L Sugars	446	(2)
Configurations of Aldoses	448	(2)
Cyclic Structures of Monosaccharides: Hemiacetal Formation	450	(2)
Monosaccharide Anomers: Mutarotation	452	(2)
Reactions of Monosaccharides	454	(6)
Polysaccharides	460	(3)
Other Important Carbohydrates	463	(1)
Cell-Surface Carbohydrates and Carbohydrate Vaccines	463	(9)
Interlude Sweetness	466	(1)
Summary and Key Words	467	(1)
Visualizing Chemistry / Additional Problems	467	(5)
Biomolecules: Amino Acids, Peptides, and Proteins	472	(35)
Structures of Amino Acids	473	(5)
Isoelectric Points	478	(3)
Peptides and Proteins	481	(1)
Covalent Bonding in Peptides	482	(2)
Peptide Structure Determination: Amino Acid Analysis	484	(1)
Peptide Sequencing: The Edman Degradation	484	(3)
Peptide Synthesis	487	(3)
Classification of Proteins	490	(1)
Protein Structure	491	(3)
Enzymes	494	(3)
How Do Enzymes Work? Citrate Synthase	497	(10)
Interlude Protein and Nutrition	500	(1)
Summary and Key Words	501	(1)
Visualizing Chemistry / Additional Problems	502	(5)
Biomolecules: Lipids and Nucleic Acids	507	(33)
Lipids	508	(1)
Fats and Oils	508	(3)
Soaps	511	(2)
Phospholipids	513	(2)
Steroids	515	(2)
Nucleic Acids and Nucleotides	517	(3)
Structure of DNA	520	(1)
Base Pairing in DNA: The Watson--Crick Model	521	(3)
Nucleic Acids and Heredity	524	(1)
Replication of DNA	524	(2)
Structure and Synthesis of RNA: Transcription	526	(1)
RNA and Protein Biosynthesis: Translation	527	(3)
Sequencing DNA	530	(2)
The Polymerase Chain Reaction	532	(8)
Interlude DNA Fingerprinting	534	(1)
Summary and Key Words	535	(1)
Visualizing Chemistry / Additional Problems	536	(4)
The Organic Chemistry of Metabolic Pathways	540	(1)
An Overview of Metabolism and Biochemical Energy	541	(3)
Catabolism of Fats: β-Oxidation Pathway	544	(5)
Catabolism of Carbohydrates: Glycolysis	549	(5)
The Citric Acid Cycle	554	(3)
Catabolism of Proteins: Transamination	557	(2)
The Organic Chemistry of Metabolic Pathways: A Summary	559	(1)
Interlude Basal Metabolism	560	(1)
Summary and Key Words	561	(1)
Visualizing Chemistry / Additional Problems	561
Appendixes
A Nomenclature of Polyfunctional Organic Compounds	1	(7)
B Glossary	8	(10)
C Answers to Selected In-Chapter Problems	18
Index	1