Organic Chemistry:Short Course

by Hart

• ISBN13: 9780395902257
• ISBN10: 0395902258
• Edition: 10th
• Format: Hardcover
• Copyright: 1999-01-01
• Publisher: Houghton Mifflin College Div

Table of Contents

Preface	xiv
To the Student	1	(5)
Bonding and Isomerism	6	(35)
How Electrons Are Arranged in Atoms	6	(2)
Ionic and Covalent Bonding	8	(4)
Ionic Compounds	9	(1)
The Covalent Bond	10	(2)
Carbon and the Covalent Bond	12	(1)
Carbon-Carbon Single Bonds	13	(1)
Polar Covalent Bonds	14	(2)
Multiple Covalent Bonds	16	(1)
Valence	17	(1)
Isomerism	18	(1)
Writing Structural Formulas	19	(2)
Abbreviated Structural Formulas	21	(2)
Formal Charge	23	(1)
Resonance	24	(2)
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	(2)
Acyclic Compounds	32	(1)
Carbocyclic Compounds	33	(1)
Heterocyclic Compounds	33	(1)
Classification According to Functional Group	34	(7)
Additional Problems	37	(4)
Alkanes and Cycloalkanes; Conformational and Geometric Isomerism	41	(30)
The Structures of Alkanes	42	(2)
Nomenclature of Organic Compounds	44	(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	(2)
A Word About: Isomers, Possible and Impossible	50	(1)
Physical Properties of Alkanes and Nonbonding Intermolecular Interactions	51	(2)
Conformations of Alkanes	53	(1)
Cycloalkane Nomenclature and Conformation	54	(5)
Cis--trans Isomerism in Cycloalkanes	59	(1)
Summary of Isomerism	60	(1)
Reactions of Alkanes	61	(3)
Oxidation and Combustion; Alkanes as Fuels	61	(1)
Halogenation of Alkanes	62	(2)
The Free-Radical Chain Mechanism of Halogenation	64	(7)
A Word About: Methane, Marsh Gas, and Miller's Experiment	64	(3)
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	77	(2)
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	82	(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	(1)
Cycloaddition to Conjugated Dienes: The Diels--Alder Reaction	97	(2)
Free-Radical Additions; Polyethylene	99	(1)
Oxidation of Alkenes	100	(4)
Oxidation with Permanganate; a Chemical Test	100	(1)
Ozonolysis of Alkenes	101	(2)
Other Alkene Oxidations	103
A Word About: Ethylene: Raw Material and Plant Hormone	102	(2)
Some Facts About Triple Bonds	104	(1)
The Orbital Model of a Triple Bond	104	(1)
Addition Reactions of Alkynes	105	(1)
Acidity of Alkynes	106	(10)
A Word About: Petroleum, Gasoline, and Octane Number	108	(2)
Reaction Summary	110	(2)
Mechanism Summary	112	(1)
Additional Problems	112	(4)
Aromatic Compounds	116	(29)
Some Facts About Benzene	117	(1)
The Kekule Structure of Benzene	118	(1)
The Resonance Model for Benzene	119	(1)
Orbital Model for Benzene	119	(1)
Symbols for Benzene	120	(1)
Nomenclature of Aromatic Compounds	121	(2)
The Resonance Energy of Benzene	123	(1)
Electrophilic Substitution	124	(1)
The Mechanism of Electrophilic Aromatic Substitution	125	(4)
Halogenation	127	(1)
Nitration	127	(1)
Sulfonation	128	(1)
Alkylation and Acylation	128	(1)
Ring-Activating and Ring-Deactivating Substituents	129	(1)
Ortho, Para-Directing, and Meta-Directing Groups	130	(4)
Ortho, Para-Directing Groups	130	(3)
Meta-Directing Groups	133	(1)
Substituent Effects on Reactivity	134	(1)
The Importance of Directing Effects in Synthesis	134	(1)
Polycyclic Aromatic Hydrocarbons	135	(10)
A Word About: Polycyclic Aromatic Hydrocarbons and Cancer	136	(2)
A Word About: C60, an Aromatic Sphere: The Fullerenes	138	(2)
Reaction Summary	140	(1)
Mechanism Summary	141	(1)
Additional Problems	141	(4)
Stereoisomerism	145	(34)
Chirality and Enantiomers	145	(2)
Stereogenic Centers; the Stereogenic Carbon Atom	147	(5)
Configuration and the R--S Convention	152	(4)
The E--Z Convention for Cis--Trans Isomers	156	(1)
Polarized Light and Optical Activity	157	(5)
A Word About: Pasteur's Experiments and the van't Hoff--LeBel Explanation	160	(2)
Properties of Enantiomers	162	(1)
Fischer Projection Formulas	163	(1)
Compounds with More Than One Stereogenic Center; Diastereomers	164	(2)
Meso Compounds; the Stereoisomers of Tartaric Acid	166	(2)
Stereochemistry: A Recap of Definitions	168	(2)
Stereochemistry and Chemical Reactions	170	(1)
Resolution of a Racemic Mixture	171	(8)
A Word About: Enantiomers and Biological Activity	172	(1)
Additional Problems	173	(6)
Organic Halogen Compounds; Substitution and Elimination Reactions	179	(25)
Nucleophilic Substitution	180	(1)
Examples of Nucleophilic Substitutions	180	(4)
Nucleophilic Substitution Mechanisms	184	(1)
The SN2 Mechanism	185	(3)
The SN1 Mechanism	188	(2)
The SN1 and SN2 Mechanisms Compared	190	(2)
Dehydrohalogenation, an Elimination Reaction; the E2 and E1 Mechanisms	192	(1)
Substitution and Elimination in Competition	193	(3)
Tertiary Halides	193	(1)
Primary Halides	194	(1)
Secondary Halides	194	(2)
A Word About: CFCs, the Ozone Layer, and Trade-offs	196	(1)
Polyhalogenated Aliphatic Compounds	196	(8)
A Word About: Insecticides and Herbicides	198	(2)
Reaction Summary	200	(1)
Mechanism Summary	200	(1)
Additional Problems	201	(3)
Alcohols, Phenols, and Thiols	204	(27)
Nomenclature of Alcohols	204	(1)
Classification of Alcohols	205	(1)
Nomenclature of Phenols	206	(1)
Hydrogen Bonding in Alcohols and Phenols	206	(2)
Acidity and Basicity Reviewed	208	(2)
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	(2)
Alcohols with More Than One Hydroxyl Group	219	(1)
Aromatic Substitution in Phenols	219	(2)
A Word About: Industrial Alcohols	220	(1)
Oxidation of Phenols	221	(3)
A Word About: Biologically Important Alcohols and Phenols	222	(2)
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	(18)
Nomenclature of Ethers	231	(1)
Physical Properties of Ethers	232	(1)
Ethers as Solvents	233	(1)
The Grignard Reagent; an Organometallic Compound	234	(2)
Preparation of Ethers	236	(2)
Cleavage of Ethers	238	(2)
A Word About: Ether and Anesthesia	239	(1)
Epoxides (Oxiranes)	240	(2)
A Word About: The Gypsy Moth's Epoxide	240	(2)
Reactions of Epoxides	242	(1)
Cyclic Ethers	243	(6)
Reaction Summary	245	(1)
Additional Problems	246	(3)
Aldehydes and Ketones	249	(34)
Nomenclature of Aldehydes and Ketones	250	(1)
Some Common Aldehydes and Ketones	251	(1)
Synthesis of Aldehydes and Ketones	252	(2)
A Word About: Quinones and the Bombardier Beetle	253	(1)
Aldehydes and Ketones in Nature	254	(1)
The Carbonyl Group	254	(2)
Nucleophilic Addition to Carbonyl Groups: An Overview	256	(2)
Addition of Alcohols: Formation of Hemiacetals and Acetals	258	(3)
Addition of Water; Hydration of Aldehydes and Ketones	261	(1)
Addition of Grignard Reagents and Acetylides	262	(2)
Addition of Hydrogen Cyanide; Cyanohydrins	264	(1)
Addition of Nitrogen Nucleophiles	265	(1)
Reduction of Carbonyl Compounds	266	(1)
Oxidation of Carbonyl Compounds	267	(2)
Keto--Enol Tautomerism	269	(2)
A Word About: Tautomerism and Photochromism	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)
Commercial Syntheses via the Aldol Condensation	275	(8)
Reaction Summary	276	(2)
Mechanism Summary	278	(1)
Additional Problems	278	(5)
Carboxylic Acids and Their Derivatives	283	(36)
Nomenclature of Acids	283	(4)
Physical Properties of Acids	287	(1)
Acidity and Acidity Constants	288	(1)
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	292	(2)
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	(1)
Carboxylic Acid Derivatives	294	(1)
Esters	295	(1)
Preparation of Esters; Fischer Esterification	296	(1)
The Mechanism of Acid-Catalyzed Esterification; Nucleophilic Acyl Substitution	296	(2)
Lactones	298	(1)
Saponification of Esters	299	(1)
Ammonolysis of Esters	300	(1)
Reaction of Esters with Grignard Reagents	300	(1)
Reduction of Esters	301	(1)
The Need for Activated Acyl Compounds	301	(1)
Acyl Halides	302	(2)
Acid Anhydrides	304	(3)
A Word About: Thioesters, Nature's Acyl-Activating Groups	306	(1)
Amides	307	(2)
A Word About: Urea	309	(1)
A Summary of Carboxylic Acid Derivatives	309	(2)
The α-Hydrogen of Esters; the Claisen Condensation	311	(8)
Reaction Summary	313	(2)
Mechanism Summary	315	(1)
Additional Problems	315	(4)
Amines and Related Nitrogen Compounds	319	(29)
Classification and Structure of Amines	319	(1)
Nomenclature of Amines	320	(2)
Physical Properties and Intermolecular Interactions of Amines	322	(1)
Preparation of Amines; Alkylation of Ammonia and Amines	323	(2)
Preparation of Amines; Reduction of Nitrogen Compounds	325	(2)
The Basicity of Amines	327	(2)
Comparison of the Basicity and Acidity of Amines and Amides	329	(1)
Reaction of Amines with Strong Acids; Amine Salts	330	(3)
A Word About: Alkaloids and the Dart-Poison Frogs	332	(1)
Chiral Amines as Resolving Agents	333	(1)
Acylation of Amines with Acid Derivatives	334	(2)
Quaternary Ammonium Compounds	336	(1)
Aromatic Diazonium Compounds	336	(3)
Diazo Coupling; Azo Dyes	339	(9)
Reaction Summary	341	(2)
Mechanism Summary	343	(1)
Additional Problems	343	(5)
Spectroscopy and Structure Determination	348	(34)
Principles of Spectroscopy	349	(1)
Nuclear Magnetic Resonance Spectroscopy (NMR)	350	(11)
Measuring an NMR Spectrum	352	(1)
Chemical Shifts and Peak Areas	352	(5)
Spin--Spin Splitting	357	(4)
C NMR Spectroscopy	361	(3)
A Word About: NMR in Biology and Medicine	362	(2)
Infrared Spectroscopy	364	(5)
Visible and Ultraviolet Spectroscopy	369	(2)
Mass Spectrometry	371	(11)
Additional Problems	375	(7)
Heterocyclic Compounds	382	(22)
Pyridine: Bonding and Basicity	382	(2)
Substitution in Pyridine	384	(3)
Other Six-Membered Heterocycles	387	(2)
Five-Membered Heterocycles: Furan, Pyrrole, and Thiophene	389	(3)
Electrophilic Substitution in Furan, Pyrrole, and Thiophene	392	(1)
Other Five-Membered Heterocycles: Azoles	393	(3)
A Word About: Porphyrins: What Makes Blood Red and Grass Green?	394	(2)
Fused-Ring Five-Membered Heterocycles: Indoles and Purines	396	(8)
A Word About: Morphine and Other Nitrogen-Containing Drugs	398	(2)
Reaction Summary	400	(1)
Mechanism Summary	401	(1)
Additional Problems	402	(2)
Synthetic Polymers	404	(25)
Classification of Polymers	404	(1)
Free-Radical Chain-Growth Polymerization	405	(6)
Cationic Chain-Growth Polymerization	411	(1)
Anionic Chain-Growth Polymerization	412	(1)
Stereoregular Polymers; Ziegler--Natta Polymerization	412	(2)
Diene Polymers: Natural and Synthetic Rubber	414	(2)
Copolymers	416	(1)
Step-Growth Polymerization: Dacron and Nylon	417	(3)
A Word About: Degradable Polymers	419	(1)
Polyurethanes and Other Step-Growth Polymers	420	(9)
A Word About: Aramids, the Latest in Polyamides	421	(3)
Reaction Summary	424	(1)
Mechanism Summary	425	(1)
Additional Problems	426	(3)
Lipids and Detergents	429	(22)
Fats and Oils; Triesters of Glycerol	429	(4)
Hydrogenation of Vegetable Oils	433	(1)
Saponification of Fats and Oils; Soap	433	(1)
How Do Soaps Work?	434	(2)
Synthetic Detergents (Syndets)	436	(4)
A Word About: Commercial Detergents	439	(1)
Phospholipids	440	(1)
Prostaglandins, Leukotrienes, and Lipoxins	440	(1)
Waxes	441	(1)
A Word About: Prostaglandins, Aspirin, and Pain	442	(1)
Terpenes and Steroids	442	(9)
Reaction Summary	447	(1)
Additional Problems	448	(3)
Carbohydrates	451	(31)
Definitions and Classification	451	(1)
Monosaccharides	452	(1)
Chirality in Monosaccharides; Fischer Projection Formulas and D,L-Sugars	453	(4)
The Cyclic Hemiacetal Structures of Monosaccharides	457	(2)
Anomeric Carbons; Mutarotation	459	(1)
Pyranose and Furanose Structures	460	(1)
Conformations of Pyranoses	461	(1)
Esters and Ethers from Monosaccharides	462	(1)
Reduction of Monosaccharides	463	(1)
Oxidation of Monosaccharides	463	(1)
Formation of Glycosides from Monosaccharides	464	(2)
Disaccharides	466	(4)
Maltose	466	(1)
Cellobiose	467	(1)
Lactose	467	(1)
Sucrose	468	(1)
A Word About: Sweetness and Sweeteners	468	(2)
Polysaccharides	470	(5)
Starch and Glycogen	470	(2)
Cellulose	472	(1)
Other Polysaccharides	473	(1)
A Word About: Fat Substitutes from Carbohydrates	474	(1)
Sugar Phosphates	475	(1)
Deoxy Sugars	475	(1)
Amino Sugars	475	(1)
Ascorbic Acid (Vitamin C)	476	(6)
Reaction Summary	477	(1)
Additional Problems	478	(4)
Amino Acids, Peptides, and Proteins	482	(37)
Naturally Occurring Amino Acids	482	(4)
A Word About: Amino Acid Dating	485	(1)
The Acid--Base Properties of Amino Acids	486	(3)
The Acid--Base Properties of Amino Acids with More Than One Acidic or Basic Group	489	(2)
Electrophoresis	491	(1)
Reactions of Amino Acids	491	(1)
The Ninhydrin Reaction	492	(1)
Peptides	492	(2)
A Word About: Some Naturally Occurring Peptides	494	(1)
The Disulfide Bond	494	(2)
Proteins	496	(1)
The Primary Structure of Proteins	496	(4)
Amino Acid Analysis	496	(1)
Sequence Determination	497	(1)
Cleavage of Selected Peptide Bonds	498	(2)
The Logic of Sequence Determination	500	(2)
Peptide Synthesis	502	(5)
A Word About: Protein Sequencing and Evolution	503	(4)
Secondary Structure of Proteins	507	(4)
Geometry of the Peptide Bond	507	(1)
Hydrogen Bonding	508	(1)
The α Helix and the Pleated Sheet	508	(3)
Tertiary Structure: Fibrous and Globular Proteins	511	(2)
Quaternary Protein Structure	513	(6)
Reaction Summary	513	(1)
Additional Problems	514	(5)
Nucleotides and Nucleic Acids	519	(26)
The General Structure of Nucleic Acids	519	(1)
Components of Deoxyribonucleic Acid (DNA)	520	(1)
Nucleosides	521	(1)
Nucleotides	522	(2)
The Primary Structure of DNA	524	(1)
Sequencing Nucleic Acids	525	(2)
A Word About: DNA and Crime	526	(1)
Laboratory Synthesis of Nucleic Acids	527	(1)
Secondary DNA Structure; the Double Helix	528	(2)
DNA Replication	530	(2)
Ribonucleic Acids; RNA	532	(1)
The Genetic Code and Protein Biosynthesis	533	(3)
Other Biologically Important Nucleotides	536	(9)
A Word About: Nucleic Acids and Viruses	538	(3)
Reaction Summary	541	(1)
Additional Problems	541	(3)
Photo Credits	544	(1)
Appendix	545	(3)
Table A: Bond energies for the dissociation of selected bonds in the reaction A---X→A · + X · (in kcal/mol)	545	(1)
Table B: Bond lengths of selected bonds (in angstroms, A)	545	(1)
Table C: Acidities of Organic Functional Groups	546	(2)
Index/Glossary	548