Organic Chemistry A Short Course

by Hart, Harold; Craine, Leslie E.; Hart, David J.

• ISBN13: 9780618215362
• ISBN10: 0618215360
• Edition: 11th
• Format: Hardcover
• Copyright: 2002-07-18
• Publisher: Brooks Cole

Table of Contents

Preface	xviii
To the Student	1	(5)
Bonding and Isomerism	6	(35)
How Electrons Are Arranged in Atoms	6	(2)
Ionic and Covalent Bonding	8	(3)
Ionic Compounds	8	(2)
The Covalent Bond	10	(1)
Carbon and the Covalent Bond	11	(2)
Carbon--Carbon Single Bonds	13	(1)
Polar Covalent Bonds	14	(1)
Multiple Covalent Bonds	15	(2)
Valence	17	(1)
Isomerism	18	(1)
Writing Structural Formulas	19	(2)
Abbreviated Structural Formulas	21	(2)
Formal Charge	23	(2)
Resonance	25	(1)
Arrow Formalism	26	(2)
The Orbital View of Bonding; the Sigma Bond	28	(1)
Carbon sp3 Hybrid Orbitals	29	(2)
Tetrahedral Carbon; the Bonding in Methane	31	(1)
Classification According to Molecular Framework	32	(1)
Acyclic Compounds	32	(1)
Carbocyclic Compounds	33	(1)
Heterocyclic Compounds	33	(1)
Classification According to Functional Group	33	(8)
Additional Problems	37	(4)
Alkanes and Cycloalkanes; Conformational and Geometric Isomerism	41	(30)
The Structures of Alkanes	41	(2)
Nomenclature of Organic Compounds	43	(1)
IUPAC Rules for Naming Alkanes	44	(2)
Alkyl and Halogen Substituents	46	(2)
Use of the IUPAC Rules	48	(1)
Sources of Alkanes	49	(1)
A Closer Look at Natural Gas	49	(1)
Physical Properties of Alkanes and Nonbonding Intermolecular Interactions	50	(2)
A Closer Look At Hydrogen Bonding	51	(1)
Conformations of Alkanes	52	(2)
Cycloalkane Nomenclature and Conformation	54	(4)
Cis--trans Isomerism in Cycloalkanes	58	(1)
Summary of Isomerism	59	(2)
A Word About Isomers, Possible and Impossible	60	(1)
Reactions of Alkanes	61	(4)
Oxidation and Combustion; Alkanes as Fuels	61	(2)
Halogenation of Alkanes	63	(1)
A Word About Methane, Marsh Gas, and Miller's Experiment	64	(1)
The Free-Radical Chain Mechanism of Halogenation	65	(6)
Reaction Summary	67	(1)
Mechanism Summary	67	(1)
Additional Problems	67	(4)
Alkenes and Alkynes	71	(45)
Definition and Classification	71	(2)
Nomenclature	73	(3)
Some Facts About Double Bonds	76	(1)
The Orbital Model of a Double Bond; the Pi Bond	76	(3)
Cis--trans Isomerism in Alkenes	79	(3)
A Word About The Chemistry of Vision	80	(2)
Addition and Substitution Reactions Compared	82	(1)
Polar Addition Reactions	82	(2)
Addition of Halogens	83	(1)
Addition of Water (Hydration)	83	(1)
Addition of Acids	84	(1)
Addition of Unsymmetric Reagents to Unsymmetric Alkenes; Markovnikov's Rule	84	(2)
Mechanism of Electrophilic Addition to Alkenes	86	(2)
Markovnikov's Rule Explained	88	(2)
Reaction Equilibrium: What Makes a Reaction Go?	90	(1)
Reaction Rates: How Fast Does a Reaction Go?	91	(3)
Hydroboration of Alkenes	94	(1)
Addition of Hydrogen	95	(1)
Additions to Conjugated Systems	96	(3)
Electrophilic Addition to Conjugated Dienes	96	(2)
Cycloaddition to Conjugated Dienes: The Diels--Alder Reaction	98	(1)
Free-Radical Additions; Polyethylene	99	(2)
Oxidation of Alkenes	101	(3)
Oxidation with Permanganate; a Chemical Test	101	(1)
Ozonolysis of Alkenes	101	(1)
A Word About Ethylene: Raw Material and Plant Hormone	102	(1)
Other Alkene Oxidations	103	(1)
Some Facts About Triple Bonds	104	(1)
The Orbital Model of a Triple Bond	104	(1)
Addition Reactions of Alkynes	105	(3)
A Word About Petroleum, Gasoline, and Octane Number	106	(2)
Acidity of Alkynes	108	(8)
A Closer Look At Petroleum	109	(1)
Reaction Summary	110	(1)
Mechanism Summary	111	(1)
Additional Problems	112	(4)
Aromatic Compounds	116	(30)
Some Facts About Benzene	117	(1)
The Kekule Structure of Benzene	118	(1)
Resonance Model for Benzene	119	(1)
Orbital Model for Benzene	119	(1)
Symbols for Benzene	120	(1)
Nomenclature of Aromatic Compounds	120	(3)
The Resonance Energy of Benzene	123	(2)
Electrophilic Aromatic Substitution	125	(1)
The Mechanism of Electrophilic Aromatic Substitution	126	(4)
Halogenation	127	(1)
Nitration	128	(1)
Sulfonation	128	(1)
Alkylation and Acylation	129	(1)
Ring-Activating and Ring-Deactivating Substituents	130	(1)
Ortho, Para-Directing, and Meta-Directing Groups	130	(5)
Ortho, Para-Directing Groups	131	(2)
Meta-Directing Groups	133	(2)
Substituent Effects on Reactivity	135	(1)
The Importance of Directing Effects in Synthesis	135	(1)
Polycyclic Aromatic Hydrocarbons	136	(10)
A Word About Polycyclic Aromatic Hydrocarbons and Cancer	137	(1)
A Word About C60, an Aromatic Sphere: The Fullerenes	138	(2)
A Closer Look At Polycyclic Aromatic Hydrocarbons	140	(1)
Reaction Summary	141	(1)
Mechanism Summary	142	(1)
Additional Problems	142	(4)
Stereoisomerism	146	(34)
Chirality and Enantiomers	146	(2)
Stereogenic Centers; the Stereogenic Carbon Atom	148	(4)
Configuration and the R--S Convention	152	(5)
The E--Z Convention for Cis--Trans Isomers	157	(1)
Polarized Light and Optical Activity	158	(4)
A Word About Pasteur's Experiments and the van't Hoff--LeBel Explanation	160	(2)
Properties of Enantiomers	162	(1)
Fischer Projection Formulas	163	(2)
Compounds with More Than One Stereogenic Center; Diastereomers	165	(2)
Meso Compounds; the Stereoisomers of Tartaric Acid	167	(2)
Stereochemistry: A Recap of Definitions	169	(1)
Stereochemistry and Chemical Reactions	170	(3)
A Word About Enantiomers and Biological Activity	172	(1)
Resolution of a Racemic Mixture	173	(7)
A Closer Look At Thalidomide	174	(1)
Additional Problems	175	(5)
Organic Halogen Compounds: Substitution and Elimination Reactions	180	(23)
Nucleophilic Substitution	180	(1)
Examples of Nucleophilic Substitutions	181	(4)
Nucleophilic Substitution Mechanisms	185	(1)
The SN2 Mechanism	185	(3)
The SN1 Mechanism	188	(2)
The SN1 and SN2 Mechanisms Compared	190	(3)
A Word About SN2 Reactions in Nature: Biological Methylations	192	(1)
Dehydrohalogenation, an Elimination Reaction; the E2 and E1 Mechanisms	193	(1)
Substitution and Elimination in Competition	194	(2)
Tertiary Halides	194	(1)
Primary Halides	195	(1)
Secondary Halides	195	(1)
Polyhalogenated Aliphatic Compounds	196	(7)
A Word About CFCs, the Ozone Layer, and Trade-Offs	198	(1)
A Word About Halogenated Organic Compounds from the Sea	199	(1)
Reaction Summary	199	(1)
Mechanism Summary	200	(1)
Additional Problems	200	(3)
Alcohols, Phenols, and Thiols	203	(28)
Nomenclature of Alcohols	203	(2)
A Word About Industrial Alcohols	205	(1)
Classification of Alcohols	205	(1)
Nomenclature of Phenols	206	(1)
Hydrogen Bonding in Alcohols and Phenols	206	(1)
Acidity and Basicity Reviewed	207	(3)
The Acidity of Alcohols and Phenols	210	(3)
The Basicity of Alcohols and Phenols	213	(1)
Dehydration of Alcohols to Alkenes	213	(2)
The Reaction of Alcohols with Hydrogen Halides	215	(1)
Other Ways to Prepare Alkyl Halides from Alcohols	216	(1)
A Comparison of Alcohols and Phenols	217	(1)
Oxidation of Alcohols to Aldehydes, Ketones, and Carboxylic Acids	217	(3)
A Word About Biologically Important Alcohols and Phenols	219	(1)
Alcohols with More Than One Hydroxyl Group	220	(1)
Aromatic Substitution in Phenols	221	(2)
A Word About Quinones and the Bombardier Beetle	222	(1)
Oxidation of Phenols	223	(1)
Phenols as Antioxidants	223	(1)
Thiols, the Sulfur Analogs of Alcohols and Phenols	224	(7)
A Word About Hair, Curly or Straight	225	(1)
Reaction Summary	226	(1)
Additional Problems	227	(4)
Ethers and Epoxides	231	(19)
Nomenclature of Ethers	232	(1)
Physical Properties of Ethers	233	(1)
Ethers as Solvents	233	(1)
The Grignard Reagent; an Organometallic Compound	234	(3)
Preparation of Ethers	237	(2)
A Closer Look at MTBE	238	(1)
Cleavage of Ethers	239	(2)
A Word About Ether and Anesthesia	240	(1)
Epoxides (Oxiranes)	241	(2)
A Word About The Gypsy Moth's Epoxide	242	(1)
Reactions of Epoxides	243	(1)
Cyclic Ethers	244	(6)
Reaction Summary	246	(1)
Additional Problems	247	(3)
Aldehydes and Ketones	250	(33)
Nomenclature of Aldehydes and Ketones	251	(1)
Some Common Aldehydes and Ketones	252	(2)
Synthesis of Aldehydes and Ketones	254	(1)
Aldehydes and Ketones in Nature	255	(1)
The Carbonyl Group	256	(1)
Nucleophilic Addition to Carbonyl Groups: An Overview	257	(1)
Addition of Alcohols: Formation of Hemiacetals and Acetals	258	(4)
Addition of Water; Hydration of Aldehydes and Ketones	262	(1)
Addition of Grignard Reagents and Acetylides	262	(3)
Addition of Hydrogen Cyanide; Cyanohydrins	265	(1)
Addition of Nitrogen Nucleophiles	266	(1)
Reduction of Carbonyl Compounds	267	(1)
Oxidation of Carbonyl Compounds	268	(2)
Keto--Enol Tautomerism	270	(1)
Acidity of α-Hydrogens; the Enolate Anion	271	(1)
Deuterium Exchange in Carbonyl Compounds	272	(1)
The Aldol Condensation	273	(2)
The Mixed Aldol Condensation	275	(1)
A Word About Water Treatment and the Chemistry of Enols/Enolates	276	(1)
Commercial Syntheses via the Aldol Condensation	276	(7)
Reaction Summary	277	(2)
Mechanism Summary	279	(1)
Additional Problems	279	(4)
Carboxylic Acids and Their Derivatives	283	(38)
Nomenclature of Acids	283	(4)
Physical Properties of Acids	287	(1)
Acidity and Acidity Constants	287	(2)
What Makes Carboxylic Acids Acidic?	289	(1)
Effect of Structure on Acidity; the Inductive Effect Revisited	290	(1)
Conversion of Acids to Salts	291	(1)
Preparation of Acids	291	(5)
Oxidation of Primary Alcohols and Aldehydes	292	(1)
Oxidation of Aromatic Side Chains	292	(1)
Reaction of Grignard Reagents with Carbon Dioxide	293	(1)
Hydrolysis of Cyanides (Nitriles)	293	(2)
A Word About Green Chemistry and Ibuprofen: A Case Study	295	(1)
A Closer Look At Green Chemistry	296	(1)
Carboxylic Acid Derivatives	296	(1)
Esters	296	(1)
Preparation of Esters; Fischer Esterification	297	(1)
The Mechanism of Acid-Catalyzed Esterification; Nucleophilic Acyl Substitution	298	(2)
Lactones	300	(1)
Saponification of Esters	300	(1)
Ammonolysis of Esters	301	(1)
Reaction of Esters with Grignard Reagents	302	(1)
Reduction of Esters	303	(1)
The Need for Activated Acyl Compounds	303	(1)
Acyl Halides	304	(2)
Acid Anhydrides	306	(3)
A Word About Thioesters, Nature's Acyl-Activating Groups	308	(1)
Amides	309	(2)
A Summary of Carboxylic Acid Derivatives	311	(1)
The α-Hydrogen of Esters; the Claisen Condensation	312	(9)
Reaction Summary	315	(1)
Mechanism Summary	316	(1)
Additional Problems	316	(5)
Amines and Related Nitrogen Compounds	321	(27)
Classification and Structure of Amines	321	(2)
Nomenclature of Amines	323	(1)
Physical Properties and Intermolecular Interactions of Amines	324	(1)
Preparation of Amines; Alkylation of Ammonia and Amines	325	(2)
Preparation of Amines; Reduction of Nitrogen Compounds	327	(2)
The Basicity of Amines	329	(2)
Comparison of the Basicity and Acidity of Amines and Amides	331	(2)
Reaction of Amines with Strong Acids; Amine Salts	333	(2)
A Word About Alkaloids and the Dart-Poison Frogs	334	(1)
Chiral Amines as Resolving Agents	335	(1)
Acylation of Amines with Acid Derivatives	336	(2)
Quaternary Ammonium Compounds	338	(1)
Aromatic Diazonium Compounds	338	(3)
Diazo Coupling; Azo Dyes	341	(7)
Reaction Summary	343	(1)
Mechanism Summary	344	(1)
Additional Problems	344	(4)
Spectroscopy and Structure Determination	348	(32)
Principles of Spectroscopy	349	(1)
Nuclear Magnetic Resonance Spectroscopy (NMR)	350	(10)
Measuring an NMR Spectrum	351	(1)
Chemical Shifts and Peak Areas	352	(4)
Spin--Spin Splitting	356	(4)
13C NMR Spectroscopy	360	(2)
A Word About NMR in Biology and Medicine	362	(1)
Infrared Spectroscopy	362	(6)
Visible and Ultraviolet Spectroscopy	368	(2)
Mass Spectrometry	370	(10)
Additional Problems	374	(6)
Heterocyclic Compounds	380	(21)
Pyridine: Bonding and Basicity	380	(2)
Substitution in Pyridine	382	(3)
Other Six-Membered Heterocycles	385	(3)
Five-Membered Heterocycles: Furan, Pyrrole, and Thiophene	388	(2)
Electrophilic Substitution in Furan, Pyrrole, and Thiophene	390	(1)
Other Five-Membered Heterocycles: Azoles	391	(2)
A Word About Porphyrins: What Makes Blood Red and Grass Green?	392	(1)
Fused-Ring Five-Membered Heterocycles: Indoles and Purines	393	(8)
A Word About Morphine and Other Nitrogen-Containing Drugs	395	(2)
Reaction Summary	397	(1)
Mechanism Summary	398	(1)
Additional Problems	398	(3)
Synthetic Polymers	401	(26)
Classification of Polymers	401	(1)
Free-Radical Chain-Growth Polymerization	402	(5)
Cationic Chain-Growth Polymerization	407	(1)
Anionic Chain-Growth Polymerization	408	(1)
Stereoregular Polymers; Ziegler--Natta Polymerization	409	(2)
A Word About Polyacetylene and Conducting Polymers	411	(1)
Diene Polymers: Natural and Synthetic Rubber	411	(2)
Copolymers	413	(1)
Step-Growth Polymerization: Dacron and Nylon	414	(5)
A Word About Degradable Polymers	416	(1)
A Word About Aramids, the Latest in Polyamides	417	(1)
A Closer Look At Nylon	418	(1)
Polyurethanes and Other Step-Growth Polymers	419	(8)
Reaction Summary	422	(1)
Mechanism Summary	423	(1)
Additional Problems	424	(3)
Lipids and Detergents	427	(21)
Fats and Oils; Triesters of Glycerol	427	(4)
Hydrogenation of Vegetable Oils	431	(1)
Saponification of Fats and Oils; Soap	431	(1)
How Do Soaps Work?	432	(1)
Synthetic Detergents (Syndets)	433	(4)
A Word About Commercial Detergents	436	(1)
Phospholipids	437	(1)
Prostaglandins, Leukotrienes, and Lipoxins	438	(2)
A Word About Prostaglandins, Aspirin, and Pain	439	(1)
Waxes	440	(1)
Terpenes and Steroids	440	(8)
Reaction Summary	445	(1)
Additional Problems	445	(3)
Carbohydrates	448	(31)
Definitions and Classification	448	(1)
Monosaccharides	449	(1)
Chirality in Monosaccharides; Fischer Projection Formulas and D,L-Sugars	450	(4)
The Cyclic Hemiacetal Structures of Monosaccharides	454	(2)
Anomeric Carbons; Mutarotation	456	(1)
Pyranose and Furanose Structures	457	(1)
Conformations of Pyranoses	458	(1)
Esters and Ethers from Monosaccharides	459	(1)
Reduction of Monosaccharides	460	(1)
Oxidation of Monosaccharides	460	(1)
Formation of Glycosides from Monosaccharides	461	(2)
Disaccharides	463	(4)
Maltose	463	(1)
Cellobiose	464	(1)
Lactose	464	(1)
Sucrose	465	(1)
A Word About Sweetness and Sweeteners	466	(1)
Polysaccharides	467	(4)
Starch and Glycogen	467	(2)
Cellulose	469	(1)
A Word About Fat Substitutes from Carbohydrates	470	(1)
Other Polysaccharides	471	(1)
Sugar Phosphates	471	(1)
Deoxy Sugars	472	(1)
Amino Sugars	472	(1)
Ascorbic Acid (Vitamin C)	472	(7)
Reaction Summary	474	(1)
Additional Problems	475	(4)
Amino Acids, Peptides, and Proteins	479	(36)
Naturally Occurring Amino Acids	479	(4)
A Word About Amino Acid Dating	482	(1)
The Acid--Base Properties of Amino Acids	483	(3)
The Acid--Base Properties of Amino Acids with More Than One Acidic or Basic Group	486	(1)
Electrophoresis	487	(1)
Reactions of Amino Acids	488	(1)
The Ninhydrin Reaction	489	(1)
Peptides	489	(3)
A Word About Some Naturally Occurring Peptides	491	(1)
The Disulfide Bond	492	(1)
Proteins	492	(1)
The Primary Structure of Proteins	492	(4)
Amino Acid Analysis	493	(1)
Sequence Determination	494	(1)
Cleavage of Selected Peptide Bonds	495	(1)
The Logic of Sequence Determination	496	(3)
A Word About Protein Sequencing and Evolution	498	(1)
Peptide Synthesis	499	(4)
Secondary Structure of Proteins	503	(3)
Geometry of the Peptide Bond	503	(1)
Hydrogen Bonding	504	(1)
The α Helix and the Pleated Sheet	504	(2)
Tertiary Structure: Fibrous and Globular Proteins	506	(2)
Quaternary Protein Structure	508	(7)
Reaction Summary	509	(1)
Additional Problems	510	(5)
Nucleotides and Nucleic Acids	515	(25)
The General Structure of Nucleic Acids	515	(1)
Components of Deoxyribonucleic Acid (DNA)	516	(1)
Nucleosides	517	(2)
Nucleotides	519	(1)
The Primary Structure of DNA	520	(1)
Sequencing Nucleic Acids	521	(2)
A Word About DNA and Crime	522	(1)
Laboratory Synthesis of Nucleic Acids	523	(1)
Secondary DNA Structure; the Double Helix	523	(3)
DNA Replication	526	(1)
Ribonucleic Acids; RNA	527	(2)
The Genetic Code and Protein Biosynthesis	529	(5)
A Word About The Human Genome	531	(1)
A Word About Nucleic Acids and Viruses	532	(2)
Other Biologically Important Nucleotides	534	(6)
Reaction Summary	537	(1)
Additional Problems	537	(3)
Photo Credits	540	(1)
Appendix	541	(3)
Table A: Bond energies for the dissociation of selected bonds in the reaction A -- X → A . + X . (in kcal/mol)	541	(1)
Table B: Bond lengths of selected bonds (in angstroms, A)	541	(1)
Table C: Typical acidities of organic functional groups	542	(2)
Index/Glossary	544