Organic Chemistry

by Smith, Janice Gorzynski

• ISBN13: 9780073101705
• ISBN10: 0073101702
• Edition: 1st
• Format: Hardcover
• Copyright: 2005-01-13
• Publisher: McGraw-Hill Science/Engineering/Math

Summary

The Smith: Organic Chemistry text brings new life to the organic chemistry world. This heavily reviewed, new text presents information in the form of bulleted lists and tables; with minimal use of text paragraphs. The author saw a great need for stepped out worked examples; incorporated biological/medicinal/environmental applications, and an art program that has yet to be seen in organic chemistry! A highlight of the art program are the micro-to-macro art pieces helping students to conceptually understand organic chemistry. Smith: Organic Chemistry is the text you need to see before you make your organic chemistry decision.

Table of Contents

List of How To's	xvii
List of Mechanisms	xviii
List of Selected Applications	xxi
Preface	xxiii
Acknowledgments	xxv
Guided Tour	xxx
Prologue 1
What Is Organic Chemistry?	2	(1)
Some Representative Organic Molecules	2	(2)
Palytoxin---An Example of a Very Complex Organic Compound	4	(2)
Structure and Bonding	6	(48)
The Periodic Table	7	(3)
Bonding	10	(2)
Lewis Structures	12	(5)
Lewis Structures Continued	17	(2)
Resonance	19	(4)
Determining Molecular Shape	23	(5)
Drawing Organic Structures	28	(4)
Hybridization	32	(5)
Ethane, Ethylene, and Acetylene	37	(5)
Bond Length and Bond Strength	42	(1)
Electronegativity and Bond Polarity	43	(2)
Polarity of Molecules	45	(2)
Capsaicin---A Representative Organic Molecule	47	(1)
Key Concepts---Structure and Bonding	47	(7)
Problems	49	(5)
Acids and Bases	54	(26)
Bronsted---Lowry Acids and Bases	55	(1)
Reactions of Bronsted--Lowry Acids and Bases	56	(2)
Acid Strength and pKa	58	(3)
Predicting the Outcome of Acid--Base Reactions	61	(1)
Factors that Determine Acid Strength	62	(8)
Common Acids and Bases	70	(1)
Aspirin	71	(1)
Lewis Acids and Bases	72	(3)
Key Concepts---Acids and Bases	75	(5)
Problems	76	(4)
Introduction to Organic Molecules and Functional Groups	80	(32)
Functional Groups	81	(1)
An Overview of Functional Groups	82	(4)
Biomolecules	86	(1)
Intermolecular Forces	86	(4)
Physical Properties	90	(7)
Application: Vitamins	97	(1)
Application of Solubility: Soap	98	(2)
Application: The Cell Membrane	100	(2)
Functional Groups and Reactivity	102	(2)
Key Concepts---Introduction to Organic Molecules and Functional Groups	104	(8)
Problems	106	(6)
Alkanes	112	(44)
Alkanes---An Introduction	113	(4)
Cycloalkanes	117	(1)
An Introduction to Nomenclature	117	(1)
Naming Alkanes	118	(6)
Naming Cycloalkanes	124	(2)
Common Names	126	(1)
Fossil Fuels	127	(1)
Physical Properties of Alkanes	128	(1)
Conformations of Acyclic Alkanes---Ethane	129	(4)
Conformations of Butane	133	(3)
An Introduction to Cycloalkanes	136	(1)
Cyclohexane	137	(3)
Substituted Cycloalkanes	140	(5)
Oxidation of Alkanes	145	(3)
Lipids---Part I	148	(1)
Key Concepts---Alkanes	149	(7)
Problems	151	(5)
Stereochemistry	156	(34)
Starch and Cellulose	157	(2)
The Two Major Classes of Isomers	159	(1)
Looking Glass Chemistry---Chiral and Achiral Molecules	160	(3)
Stereogenic Centers	163	(2)
Stereogenic Centers in Cyclic Compounds	165	(2)
Labeling Stereogenic Centers with R or S	167	(4)
Diastereomers	171	(2)
Meso Compounds	173	(2)
R and S Assignments in Compounds with Two or More Stereogenic Centers	175	(1)
Disubstituted Cycloalkanes	176	(1)
Isomers---A Summary	177	(1)
Physical Properties of Stereoisomers	178	(4)
Chemical Properties of Enantiomers	182	(2)
Key Concepts---Stereochemistry	184	(6)
Problems	185	(5)
Understanding Organic Reactions	190	(30)
Writing Equations for Organic Reactions	191	(1)
Kinds of Organic Reactions	192	(2)
Bond Breaking and Bond Making	194	(4)
Bond Dissociation Energy	198	(3)
Thermodynamics	201	(2)
Enthalpy and Entropy	203	(2)
Energy Diagrams	205	(2)
Energy Diagram for a Two-Step Reaction Mechanism	207	(3)
Kinetics	210	(2)
Catalysts	212	(1)
Enzymes	213	(1)
Key Concepts---Understanding Organic Reactions	214	(6)
Problems	216	(4)
Alkyl Halides and Nucleophilic Substitution	220	(50)
Introduction to Alkyl Halides	221	(1)
Nomenclature	222	(1)
Physical Properties	223	(1)
Interesting Alkyl Halides	224	(2)
The Polar Carbon--Halogen Bond	226	(1)
General Features of Nucleophilic Substitution	226	(2)
The Leaving Group	228	(2)
The Nucleophile	230	(4)
Possible Mechanisms for Nucleophilic Substitution	234	(1)
Two Mechanisms for Nucleophilic Substitution	235	(1)
The SN2 Mechanism	236	(5)
Application: Useful SN2 Reactions	241	(3)
The SN1 Mechanism	244	(4)
Carbocation Stability	248	(2)
The Hammond Postulate	250	(3)
Application: SN1 Reactions, Nitrosamines, and Cancer	253	(1)
When Is the Mechanism SN1 or SN2?	254	(5)
Vinyl Halides and Aryl Halides	259	(1)
Organic Synthesis	260	(2)
Key Concepts---Alkyl Halides and Nucleophilic Substitution	262	(8)
Problems	263	(7)
Alkyl Halides and Elimination Reactions	270	(32)
General Features of Elimination	271	(2)
Alkenes---The Products of Elimination Reactions	273	(4)
The Mechanisms of Elimination	277	(1)
The E2 Mechanism	277	(4)
The Zaitsev Rule	281	(2)
The El Mechanism	283	(2)
SN1 and E1 Reactions	285	(2)
Stereochemistry of the E2 Reaction	287	(2)
When Is the Mechanism E1 or E2?	289	(1)
E2 Reactions and Alkyne Synthesis	290	(2)
When Is the Reaction SN1, SN2, E1, or E2?	292	(4)
Key Concepts---Alkyl Halides and Elimination Reactions	296	(6)
Problems	297	(5)
Alcohols, Ethers, and Epoxides	302	(44)
Introduction	303	(1)
Structure and Bonding	304	(1)
Nomenclature	304	(3)
Physical Properties	307	(1)
Interesting Alcohols, Ethers, and Epoxides	308	(3)
Preparation of Alcohols, Ethers, and Epoxides	311	(2)
General Features---Reactions of Alcohols, Ethers, and Epoxides	313	(1)
Dehydration of Alcohols to Alkenes	314	(4)
Carbocation Rearrangements	318	(2)
Dehydration Using POCI3 and Pyridine	320	(2)
Conversion of Alcohols to Alkyl Halides with HX	322	(3)
Conversion of Alcohols to Alkyl Halides with SOCI2 and PBr3	325	(2)
Tosylate---Another Good Leaving Group	327	(3)
Reaction of Ethers with Strong Acid	330	(2)
Reaction of Epoxides	332	(4)
Application: Epoxides, Leukotrienes, and Asthma	336	(1)
Application: Benzo[a]pyrene, Epoxides, and Cancer	337	(1)
Key Concepts---Alcohols, Ethers, and Epoxides	338	(8)
Problems	340	(6)
Alkenes	346	(40)
Introduction	347	(1)
Calculating Degrees of Unsaturation	348	(1)
Nomenclature	349	(4)
Physical Properties	353	(1)
Interesting Alkenes	353	(1)
Lipids---Part 2	354	(2)
Preparation of Alkenes	356	(1)
Introduction to Addition Reactions	357	(1)
Hydrohalogenation---Electrophilic Addition of HX	358	(3)
Markovnikov's Rule	361	(2)
Stereochemistry of Electrophilic Addition of HX	363	(2)
Hydration---Electrophilic Addition of Water	365	(1)
Halogenation---Addition of Halogen	366	(2)
Stereochemistry of Halogenation	368	(2)
Halohydrin Formation	370	(3)
Hydroboration--Oxidation	373	(4)
Keeping Track of Reactions	377	(1)
Alkenes in Organic Synthesis	378	(2)
Key Concepts---Alkenes	380	(6)
Problems	381	(5)
Alkynes	386	(26)
Introduction	387	(1)
Nomenclature	388	(1)
Physical Properties	389	(1)
Interesting Alkynes	389	(2)
Preparation of Alkynes	391	(1)
Introduction to Alkyne Reactions	392	(1)
Addition of Hydrogen Halides	393	(2)
Addition of Halogen	395	(1)
Addition of Water	396	(3)
Hydroboration--Oxidation	399	(2)
Reaction of Acetylide Anions	401	(3)
Synthesis	404	(3)
Key Concepts---Alkynes	407	(5)
Problems	408	(4)
Oxidation and Reduction	412	(34)
Introduction	413	(1)
Reducing Agents	414	(1)
Reduction of Alkenes	415	(3)
Application: Hydrogenation of Oils	418	(1)
Reduction of Alkynes	419	(3)
The Reduction of Polar C--X σ Bonds	422	(1)
Oxidizing Agents	423	(2)
Epoxidation	425	(3)
Dihydroxylation	428	(2)
Oxidative Cleavage of Alkenes	430	(2)
Oxidative Cleavage of Alkynes	432	(1)
Oxidation of Alcohols	433	(3)
Application: The Oxidation of Ethanol	436	(1)
Sharpless Epoxidation	436	(3)
Key Concepts---Oxidation and Reduction	439	(7)
Problems	441	(5)
Radical Reactions	446	(32)
Introduction	447	(1)
General Features of Radical Reactions	448	(2)
Halogenation of Alkanes	450	(1)
The Mechanism of Halogenation	451	(2)
Chlorination of Other Alkanes	453	(1)
Chlorination versus Bromination	454	(3)
Halogenation as a Tool in Organic Synthesis	457	(1)
The Stereochemistry of Halogenation Reactions	457	(2)
Application: The Ozone Layer and CFCs	459	(2)
Redical Halogenation at an Allylic Carbon	461	(4)
Application: Oxidation of Unsaturated Lipids	465	(1)
Application: Antioxidants	466	(1)
Radical Addition Reactions to Double Bonds	467	(3)
Polymers and Polymerization	470	(2)
Key Concepts---Radical Reactions	472	(6)
Problems	473	(5)
Mass Spectrometry and Infrared Spectroscopy	478	(26)
Mass Spectrometry	479	(4)
Alkyl Halides and the M + 2 Peak	483	(1)
Other Types of Mass Spectrometry	484	(3)
Electromagnetic Radiation	487	(1)
Infrared Spectroscopy	488	(2)
IR Absorptions	490	(7)
IR and Structure Determination	497	(2)
Key Concepts---Mass Spectrometry and Infrared Spectroscopy	499	(5)
Problems	500	(4)
Nuclear Magnetic Resonance Spectroscopy	504	(40)
An Introduction to NMR Spectroscopy	505	(3)
1H NMR: Number of Signals	508	(3)
1H NMR: Position of Signals	511	(3)
The Chemical Shift of Protons on sp2 and sp Hybridized Carbons	514	(2)
1H NMR: Intensity of Signals	516	(2)
1H NMR: Spin--Spin Splitting	518	(4)
More Complex Examples of Splitting	522	(3)
Spin--Spin Splitting in Alkenes	525	(2)
Other Facts About 1H NMR Spectroscopy	527	(2)
Using 1H NMR to Identify an Unknown	529	(2)
13C NMR Spectroscopy	531	(4)
Magnetic Resonance Imaging (MRI)	535	(1)
Key Concepts---Nuclear Magnetic Resonance Spectroscopy	536	(8)
Problems	537	(7)
Conjugation, Resonance, and Dienes	544	(34)
Conjugation	545	(2)
Resonance and Allylic Carbocations	547	(1)
Common Examples of Resonance	548	(2)
The Resonance Hybrid	550	(1)
Electron Delocalization, Hybridization, and Geometry	551	(1)
Conjugated Dienes	552	(1)
Interesting Dienes and Polyenes	553	(1)
The Carbon--Carbon σ Bond Length in 1,3-Butadiene	553	(2)
Stability of Conjugated Dienes	555	(1)
Electrophilic Addition: 1,2-Versus, 1,4-Addition	556	(2)
Kinetic Versus Thermodynamic Products	558	(3)
The Diels--Alder Reaction	561	(2)
Specific Rules Governing the Diels--Alder Reaction	563	(4)
Other Facts About the Diels--Alder Reaction	567	(2)
Conjugated Dienes and Ultraviolet Light	569	(2)
Key Concepts---Conjugation, Resonance, and Dienes	571	(7)
Problems	571	(7)
Benzene and Aromatic Compounds	578	(30)
Background	579	(1)
The Structure of Benzene	580	(1)
Nomenclature of Benzene Derivatives	581	(2)
Spectroscopic Properties	583	(1)
Interesting Aromatic Compounds	584	(1)
Benzene's Unusual Stability	585	(2)
The Criteria for Aromaticity---Huckel's Rule	587	(3)
Examples of Aromatic Compounds	590	(6)
What Is the Basis of Huckel's Rule?	596	(2)
The Inscribed Polygon Method for Predicting Aromaticity	598	(3)
Buckminsterfullerene---Is It Aromatic?	601	(1)
Key Concepts---Benzene and Aromatic Compounds	602	(6)
Problems	602	(6)
Electrophilic Aromatic Substitution	608	(44)
Electrophilic Aromatic Substitution	609	(1)
The General Mechanism	609	(3)
Halogenation	612	(1)
Nitration and Sulfonation	613	(1)
Friedel--Crafts Alkylation and Friedel--Crafts Acylation	614	(6)
Substituted Benzenes	620	(4)
Electrophilic Aromatic Substitution of Substituted Benzenes	624	(2)
Why Substituents Activate or Deactivate a Benzene Ring	626	(2)
Orientation Effects in Substituted Benzenes	628	(3)
Limitations on Electrophilic Substitution Reactions with Substituted Benzenes	631	(2)
Disubstituted Benzenes	633	(2)
Synthesis of Benzene Derivatives	635	(1)
Halogenation of Alkyl Benzenes	636	(2)
Oxidation and Reduction of Substituted Benzenes	638	(3)
Multistep Synthesis	641	(3)
Key Concepts---Electrophilic Aromatic Substitution	644	(8)
Problems	646	(6)
Carboxylic Acids and the Acidity of the O--H Bond	652	(32)
Structure and Bonding	653	(1)
Nomenclature	654	(3)
Physical Properties	657	(1)
Spectroscopic Properties	658	(1)
Interesting Carboxylic Acids	659	(1)
Aspirin, Arachidonic Acid, and Prostaglandins	660	(1)
Preparation of Carboxylic Acids	661	(2)
Reactions of Carboxylic Acids---General Features	663	(1)
Carboxylic Acids---Strong Organic Bronsted--Lowry Acids	664	(3)
Inductive Effects in Aliphatic Carboxylic Acids	667	(1)
Substituted Benzoic Acids	668	(2)
Extraction	670	(3)
Sulfonic Acids	673	(1)
Amino Acids	673	(3)
Key Concepts---Carboxylic Acids and the Acidity of the O--H Bond	676	(8)
Problems	678	(6)
Introduction to Carbonyl Chemistry; Organometallic Reagents; Oxidation and Reduction	684	(48)
Introduction	685	(1)
General Reactions of Carbonyl Compounds	686	(3)
A Preview of Oxidation and Reduction	689	(1)
Reduction of Aldehydes and Ketones	690	(3)
The Stereochemistry of Carbonyl Reduction	693	(1)
Enantioselective Carbonyl Reductions	693	(3)
Reduction of Carboxylic Acids and Their Derivatives	696	(4)
Oxidation of Aldehydes	700	(1)
Organometallic Reagents	701	(3)
Reaction of Organometallic Reagents with Aldehydes and Ketones	704	(3)
Retrosynthetic Analysis of Grignard Products	707	(2)
Protecting Groups	709	(2)
Reaction of Organometallic Reagents with Carboxylic Acid Derivatives	711	(3)
Reaction of Organometallic Reagents with Other Compounds	714	(2)
α,β-Unsaturated Carbonyl Compounds	716	(3)
Summary---The Reactions of Organometallic Reagents	719	(1)
Synthesis	719	(3)
Key Concepts---Introduction to Carbonyl Chemistry; Organometallic Reagents; Oxidation and Reduction	722	(10)
Problems	725	(7)
Aldehydes and Ketones---Nucleophilic Addition	732	(48)
Introduction	733	(1)
Nomenclature	734	(3)
Physical Properties	737	(1)
Spectroscopic Properties	738	(2)
Interesting Aldehydes and Ketones	740	(1)
Preparation of Aldehydes and Ketones	741	(2)
Reactions of Aldehydes and Ketones---General Considerations	743	(2)
Nucleophilic Addition of H- and R- ---A Review	745	(3)
Nucleophilic Addition of -CN	748	(1)
The Wittig Reaction	749	(5)
Addition of 1 Amines	754	(2)
Addition of 2 Amines	756	(3)
Addition of H2O---Hydration	759	(3)
Addition of Alcohols---Acetal Formation	762	(3)
Acetals as Protecting Groups	765	(1)
Cyclic Hemiacetals	766	(3)
An Introduction to Carbohydrates	769	(2)
Key Concepts---Aldehydes and Ketones---Nucleophilic Addition	771	(9)
Problems	773	(7)
Carboxylic Acids and Their Derivatives---Nucleophilic Acyl Substitution	780	(52)
Introduction	781	(2)
Structure and Bonding	783	(2)
Nomenclature	785	(3)
Physical Properties	788	(1)
Spectroscopic Properties	789	(1)
Interesting Esters and Amides	790	(2)
Introduction to Nucleophilic Acyl Substitution	792	(4)
Reactions of Acid Chlorides	796	(1)
Reactions of Anhydrides	797	(2)
Reactions of Carboxylic Acids	799	(5)
Reactions of Esters	804	(2)
Application: Lipid Hydrolysis	806	(2)
Reactions of Amides	808	(1)
Application: The Mechanism of Action of β-Lactam Antibiotics	809	(1)
Summary of Nucleophilic Acyl Substitution Reactions	810	(1)
Natural and Synthetic Fibers	811	(2)
Biological Acylation Reactions	813	(2)
Nitriles	815	(5)
Key Concepts---Carboxylic Acids and Their Derivatives---Nucleophilic Acyl Substitution	820	(12)
Problems	823	(9)
Substitution Reactions of Carbonyl Compounds at the α Carbon	832	(32)
Introduction	833	(1)
Enols	834	(2)
Enolates	836	(5)
Enolates of Unsymmetrical Carbonyl Compounds	841	(2)
Racemization at the α Carbon	843	(1)
A Preview of Reactions at the α Carbon	844	(1)
Halogenation at the α Carbon	844	(4)
Direct Enolate Alkylation	848	(3)
Malonic Ester Synthesis	851	(4)
Acetoacetic Ester Synthesis	855	(3)
Key Concepts---Substitution Reactions of Carbonyl Compounds at the α Carbon	858	(6)
Problems	859	(5)
Carbonyl Condensation Reactions	864	(28)
The Aldol Reaction	865	(4)
Crossed Aldol Reactions	869	(3)
Directed Aldol Reactions	872	(1)
Intramolecular Aldol Reactions	873	(2)
The Claisen Reaction	875	(2)
The Crossed Claisen and Related Reactions	877	(2)
The Dieckmann Reaction	879	(1)
The Michael Reaction	880	(2)
The Robinson Annualation	882	(3)
Key Concepts---Carbonyl Condensation Reactions	885	(7)
Problems	887	(5)
Amines	892	(50)
Introduction	893	(1)
Structure and Bonding	894	(1)
Nomenclature	895	(2)
Physical Properties	897	(1)
Spectroscopic Properties	898	(1)
Interesting and Useful Amines	899	(4)
Preparation of Amines	903	(6)
Reactions of Amines---General Features	909	(1)
Amines as Bases	909	(2)
Relative Basicity of Amines and Other Compounds	911	(6)
Amines as Nucleophiles	917	(2)
Hofmann Elimination	919	(3)
Reaction of Amines with Nitrous Acid	922	(2)
Substitution Reactions of Aryl Diazonium Salts	924	(4)
Coupling Reactions of Aryl Diazonium Salts	928	(2)
Application: Perkin's Mauveine and Synthetic Dyes	930	(2)
Application: Sulfa Drugs	932	(1)
Key Concepts---Amines	933	(9)
Problems	935	(7)
Lipids	942	(28)
Introduction	943	(1)
Waxes	944	(1)
Triacylglycerols	944	(4)
Phospholipids	948	(2)
Fat-soluble Vitamins	950	(2)
Eicosanoids	952	(3)
Terpenes	955	(5)
Steroids	960	(4)
Key Concepts---Lipids	964	(6)
Problems	965	(5)
Carbohydrates	970	(42)
Introduction	971	(1)
Monosaccharides	972	(4)
The Family of D-Aldoses	976	(2)
The Family of D-Ketoses	978	(1)
Physical Properties of Monosaccharides	978	(1)
The Cyclic Forms of Monosaccharides	979	(5)
Glycosides	984	(3)
Reactions of Monosaccharides at the OH Groups	987	(1)
Reactions at the Carbonyl Group---Oxidation and Reduction	988	(3)
Reactions at the Carbonyl Group---Adding or Removing One Carbon Atom	991	(3)
The Fischer Proof of the Structure of Glucose	994	(3)
Disaccharides	997	(2)
Polysaccharides	999	(2)
Other Important Sugars and Their Derivatives	1001	(4)
Key Concepts---Carbohydrates	1005	(7)
Problems	1007	(5)
Amino Acids and Proteins	1012
Amino Acids	1013	(3)
Synthesis of Amino Acids	1016	(3)
Separation of Amino Acids	1019	(4)
Enantioselective Synthesis of Amino Acids	1023	(1)
Peptides	1024	(4)
Peptide Synthesis	1028	(4)
Automated Peptide Synthesis	1032	(3)
Protein Structure	1035	(5)
Important Proteins	1040	(3)
Key Concepts---Amino Acids and Proteins	1043
Problems	1044
Appendix A Common Abbreviations, Arrows, and Symbols	1	(2)
Appendix B pKa, Values for Selected Compounds	3	(2)
Appendix C Bond Dissociation Energies for Some Common Bonds	5	(2)
Appendix D Characteristic IR Absorption Frequencies	7	(2)
Appendix E Characteristic 1H NMR Absorptions	9	(2)
Appendix F General Types of Organic Reactions	11	(2)
Appendix G How to Synthesize Particular Functional Groups	13	(4)
Appendix H Reactions that Form Carbon--Carbon Bonds	17
Glossary	1	(1)
Credits	1	(1)
Index	1