Table Of ContentTHEORY AND PROBLEMS OF
Third Edition
MEISLICH, Ph.D. HOWARD NECHAMKIN, Ed.D.
Professor Emeritus of Chemistry
Trenton State College
AREFKIN, Ph.D. GEORGE J. HADEMENOS, Ph.D.
Visiting Assistant Professor
Department of Physics
University of Dallas
Schaum’s Outline Series
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HERBERT MEISLICH holds a B.A. degree from Brooklyn College and an M.A. and Ph.D. from Columbia
University. He is a professor emeritus from the City College of CUNY, where he taught Organic and General
Chemistry for forty years at both the undergraduate and doctoral levels. He received the Outstanding Teacher
award in 1985, and has coauthored eight textbooks, three laboratory manuals in General and Organic Chemistry,
and 15 papers on his research interests.
HOWARD NECHAMKIN is Professor Emeritus of Chemistry at Trenton State College; for 11 years of his
tenure he served as Department Chairman. His Bachelor’s degree is from Brooklyn College, his Master’s from
the Polytechnic Institute of Brooklyn and his Doctorate in Science Education from New York University. He is
the author or coauthor of 53 papers and 6 books in the areas of inorganic, analytical, and environmental
chemistry.
JACOB SHAREFKIN is Professor Emeritus of Chemistry at Brooklyn College. After receiving a B.S. from
City College of New York, he was awarded an M.A. from Columbia University and a Ph.D. from New York
University. His publications and research interest in Qualitative Organic Analysis and organic boron and iodine
compounds have been supported by grants from the American Chemical Society, for whom he has also
designed national examinations in Organic Chemistry.
GEORGE J. HADEMENOS is a Visiting Assistant Professor of Physics at the University of Dallas. He
received his B.S. with a combined major of physics and chemistry from Angelo State University, his M.S. and
Ph.D. in physics from the University of Texas at Dallas, and completed postdoctoral fellowships in nuclear
medicine at the University of Massachusetts Medical Center and in radiological sciences/biomedical physics at
UCLA Medical Center. His research interests have involved biophysical and biochemical mechanisms of
disease processes, particularly cerebrovascular diseases and stroke. He has published his work in journals such
as American Scientist, Physics Today, Neurosurgery, and Stroke. In addition, he has written three books: Physics
of Cerebrovascular Diseases: Biophysical Mechanisms of’ Development, Diagnosis, and Therap-y, published by
Springer-Verlag; Schaum S Outline of Physics jor Pre-Med, Biolog,v, und Allied Health Students, and Schaum S
Outline of Biology, coauthored with George Fried, Ph.D., both published by McGraw-Hill. Among other
courses, he teaches general physics for biology and pre-med students.
Schaum’s Outline of Theory and Problems of
ORGANIC CHEMISTRY
Copyright 0 1999, 1991, 1977 by The McGraw-Hill Companies, Inc. All rights reserved. Printed
in the United States of America. Except as permitted under the Copyright Act of 1976, no part of
this publication may be reproduced or distributed in any form or by any means, or stored in a data
base or retrieval system, without the prior written permission of the publisher.
2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 PRS PRS 9 0 2 I 0 9
ISBN 0-07-134165-x
Sponsoring Editor: Barbara Gilson
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Library of Congress Cataloging-in-Publication Data
Schaum’s outline of theory and problems of organic chemistry / Herbert
Meislich ... [et al.]. -- 3rd ed.
p. cm. -- (Schaum’s outline series)
Includes index.
ISBN 0-07-134165-X
1. Chemistry, Organic--Problems, exercises, etc. 2. Chemistry,
Organic--Outlines, syllabi, etc. I. Meislich, Herbert. 11. Title:
Theory and problems of organic chemistry. 111. Title: Organic
Chemistry,
QD257.M44 1999
547--dc21 99-2858 1
PID
McGraw-Hill ELll
A Division of TheMcGmw-HiUCompanies
To Amy Nechamkin, Belle D. Sharefkin,
John 6.Sharefkin,
Kelly Hademenos, and Alexandra Hademenos
The beginning student in Organic Chemistry is often overwhelmed by facts, concepts, and new language.
Each year, textbooks of Organic Chemistry grow in quantity of subject matter and in level of sophistication.
This Schaum’s Outline was undertaken to give a clear view of first-year Organic Chemistry through the careful
detailed solution of illustrative problems. Such problems make up over 80% of the book, the remainder being a
concise presentation of the material. Our goal is for students to learn by thinking and solving problems rather
than by merely being told.
This book can be used in support of a standard text, as a supplement to a good set of lecture notes, as a
review for taking professional examinations, and as a vehicle for self-instruction.
The second edition has been reorganized by combining chapters to emphasize the similarities of fhctional
groups and reaction types as well as the differences. Thus, polynuclear hydrocarbons are combined with
benzene and aromaticity. Nucleophilic aromatic displacement is merged with aromatic substitution. Sulfonic
acids are in the same chapter with carboxylic acids and their derivatives, and carbanion condensations are in a
separate new chapter. Sulfur compounds are discussed with their oxygen analogs. This edition has also been
brought up to date by including solvent effects, CMR spectroscopy, an elaboration of polymer chemistry, and
newer concepts of stereochemistry, among other material.
HERBERTMEISLICH
HOWARDNECHAMKIN
JACOBSHAREFKIN
GEORGEJ. HADEMENOS
CHAPTER 9. STRUCTURE AND PROPERTIES OF ORGANIC
COMPOUNDS 1
1
1.1
Carbon Compounds
1.2
Lewis Structural Formulas 2
I .3
Types of Bonds 6
6
1.4
Functional Groups
7
1.5
Formal Charge
CHAPTER 2 BONDING AND MOLECULAR STRUCTURE 13
13
2.1 Atomic Orbitals
14
2.2 Covalent Bond Formation-Molecular Orbital (MO) Method
17
2.3 Hybridization of Atomic Orbitals
21
2.4 Electronegativity and Polarity
21
2.5 Oxidation Number
22
2.6 Intermolecular Forces
22
2.7 Solvents
2.8 Resonance and Delocalized n Electrons 23
CHAPTER 3 CHEMICAL REACTIVITY AND ORGANIC REACTIONS 31
31
3.1 Reaction Mechanism
31
3.2 Carbon-Containing Intermediates
33
3.3 Types of Organic Reactions
35
3.4 Electrophilic and Nucleophilic Reagents
36
3.5 Thermodynamics
37
3.6 Bond-Dissociation Energies
37
3.7 Chemical Equilibrium
39
3.8 Rates of Reactions
39
3.9 Transition-State Theory and Enthalpy Diagrams
42
3.10 Bronsted Acids and Bases
43
3.1 1 Basicity (Acidity) and Structure
44
3.12 Lewis Acids and Bases
50
CHAPTER 4 ALKANES
50
4.1 Definition
54
4.2 Nomenclature of Alkanes
56
4.3 Preparation of Alkanes
58
4.4 Chemical Properties of Alkanes
62
4.5 Summary of Alkane Chemistry
CONTENTS
CHAPTER 5 STEREOCHEMI STRY 69
5.1 Stereoisomerism 69
5.2 Optical Isomerism 70
5.3 Relative and Absolute Configuration 72
5.4 Molecules with More Than One Chiral Center 77
5.5 Synthesis and Optical Activity 79
CHAPTER 6 ALKENES 87
6.1 Nomenclature and Structure 87
6.2 Geometric (cis-tram)Isomerism 88
6.3 Preparation of Alkenes 91
6.4 Chemical Properties of Alkenes 95
6.5 Substitution Reactions at the Allylic Position 105
6.6 Summary of Alkene Chemistry
107
CHAPTER 7 ALKYL HALIDES
118
7.1 Introduction
118
7.2 Synthesis of RX
119
7.3 Chemical Properties
121
7.4 Summary of Alkyl Halide Chemistry
132
CHAPTER $ ALKYNES AND DIENES
140
8.1 Alkynes
140
8.2 Chemical Properties of Acetylenes
143
8.3 Alkadienes
146
8.4 MO Theory and Delocalized n: Systems
147
8.5 Addition Reactions of Conjugated Dienes
149
8.6 Polymerization of Dienes
153
8.7 Cy cloaddition
154
8.8 Summary of Alkyne Chemistry
154
8.9 Summary of Diene Chemistry
154
CHAPTER 9 CYCLIC HYDROCARBONS
162
9.1 Nomenclature and Structure
162
9.2 Geometric Isomerism and Chirality
163
9.3 Conformations of Cycloalkanes
166
9.4 Synthesis
173
9.5 Chemistry
175
9.6 MO Theory of Pericyclic Reactions
177
9.7 Terpenes and the Isoprene Rule
181
CONTENTS
CHAPTER 10 BENZENE AND POLYNUCLEAR AROMATIC
COMPOUNDS 189
10.1 Introduction 189
10.2 Aromaticity and Huckel’s Rule 193
10.3 Antiaromaticity 194
10.4 Polynuclear Aromatic Compounds 197
10.5 Nomenclature 198
10.6 Chemical Reactions 199
10.7 Synthesis 202
CHAPTER 12 AROMATIC SUBSTITUTION. ARENES 205
11.1 Aromatic Substitution by Electrophiles (Lewis Acids, E+
or E) 205
1 1.2 Electrophilic Substitutions in Syntheses of Benzene
Derivatives 214
11.3 Nucleophilic Aromatic Substitutions 215
11.4 Arenes 218
11.5 Summary of Arene and Aryl Halide Chemistry 223
CHAPTER 12 SPECTROSCOPY AND STRUCTURE 230
12 .1 Introduction 230
12.2 Ultraviolet and Visible Spectroscopy 23 1
12.3 Infrared Spectroscopy 233
12.4 Nuclear Magnetic Resonance (Proton, PMR) 236
12.5 13C NMR (CMR) 245
12.6 Mass Spectroscopy 247
CHAPTER 13 ALCOHOLS AND THIOLS 256
A. Alcohols 256
13.1 Nomenclature and H-Bonding 256
13.2 Preparation 258
13.3 Reactions 262
13.4 Summary of Alcohol Chemistry 266
B. Thiols 267
13.5 General 267
13.6 Summary of Thiol Chemistry 268
CHAPTER 24 ETHERS, EPOXIDES, GLYCOLS, AND THIOETHERS 278
A. Ethers 278
14.1 Introduction and Nomenclature 278
CONTENTS
14.2 Preparation 279
14.3 Chemical Properties 282
14.4 Cyclic Ethers 285
14.5 Summary of Ether Chemistry 286
B. Epoxides 287
14.6 Introduction 287
14.7 Synthesis 287
14.8 Chemistry 288
14.9 Summary of Epoxide Chemistry 290
C. Glycols 29 1
14.10 Preparation of 1,2-Glycols 29 1
14.11 Unique Reactions of Glycols 292
14.12 Summary of Glycol Chemistry 294
D. Thioethers 294
14.13 Introduction 294
14.14 Preparation 295
14.15 Chemistry 295
CHAPTER 15 CARBONYL COMPOUNDS: ALDEHYDES AND KETONE 302
15.1 Introduction and Nomenclature 302
15.2 Preparation 305
3 10
15.3 Oxidation and Reduction \
15.4 Addition Reactions of Nucleophiles to ,C=O 313
15.5 Addition of Alcohols: Acetal and Ketal Formation 317
15.6 Attack by Ylides; Wittig Reaction 319
15.7 Miscellaneous Reactions 321
15.8 Summary of Aldehyde Chemistry 323
15.9 Summary of Ketone Chemistry 324
CHAPTER 16 CARBOXYLIC ACIDS AND THEIR DERIVATIVES 331
16.1 Introduction and Nomenclature 331
16.2 Preparation of Carboxylic Acids 334
16.3 Reactions of Carboxylic Acids 336
16.4 Summary of Carboxylic Acid Chemistry 342
16.5 Polyfunctional Carboxylic Acids 342
16.6 Transacylation; Interconversion of Acid Derivatives 346
16.7 More Chemistry of Acid Derivatives 349
16.8 Summary of Carboxylic Acid Derivative Chemistry 356
16.9 Analytical Detection of Acids and Derivatives 356
16.10 Carbonic Acid Derivatives 358
16.11 Summary of Carbonic Acid Derivative Chemistry 359
16.12 Synthetic Condensation Polymers 360
16.13 Derivatives of Sulfonic Acids 361
CONTENTS
CARBANION-ENOLATES AND ENOLS 373
17.1 Acidity of H’s a to C=O; Tautomerism 373
17.2 Alkylation of Simple Carbanion-Enolates 377
17.3 Alkylation of Stable Carbanion-Enolates 380
17 .4 Nucleophilic Addition to Conjugated Carbonyl Compounds:
Michael 3’4-Addition 385
17.5 Condensations 386
400
18.1 Nomenclature and Physical Properties 400
18.2 Preparation 402
18.3 Chemical Properties 407
18.4 Reactions of Quaternary Ammonium Salts 413
18.5 Ring Reactions of Aromatic Arnines 414
18.6 Spectral Properties 416
18.7 Reactions of Aryl Diazonium Salts 416
18.8 Summary of Amine chemistry 419
PHENOLIC COMPOUNDS 430
19.1 Introduction 430
19 .2 Preparation 43 1
19.3 Chemical Properties 433
19.4 Analytical Detection of Phenols 440
19.5 Summary of Phenolic Chemistry 44 1
19.6 Summary of Phenolic Ethers and Esters 44 1
2 AROMATIC H ETEROCY CLIC COM POU N DS 448
~~~~~~~
20.1 Five-Membered Aromatic Heterocycles with One Heteroatom 448
20.2 Six-Membered Heterocycles with One Heteroatom 454
20.3 Compounds with Two Heteroatoms 458
20.4 Condensed Ring Systems 458
INDEX 465
!-
Structure
and
Properties o f
Organic Compounds
ON COMPOUNDS
Orgatuc chemistry is the study of carbon (C) compounds, all of which have covalent bonds. Carbon atoms
can bond to each other to form open-chain compounds, Fig. l-l(u), or cyclic (ring) compounds, Fig.
1-1 (c). Both types can also have branches of C atoms, Fig. 1-1(b) and (6).Saturated compounds have C’s
bonded to each other by single bonds, C-C; unsaturated compounds have C’s joined by multiple bonds.
Exampleswith double bonds and triple bonds are shown in Fig. I-l(e). Cyclic compounds having at least
one atom in the ring other than C (a heteroatom) are called heterocyclics, Fig. 1 - 1 0 The heteroatoms
are usually oxygen (0),nitrogen (N), or sulhr (S).
Iaroblem 1.1 Why are there so many compounds that contain carbon? 4
Bonds between C’s are covalent and strong, so that C’s can form long chains and rings, both of which may have
branches. C’s can bond to almost every element in the periodic table. Also, the number of isomers increases as the
oreanic molecules become more complex.
I3roblem 1.2 CC5mpare and contrast the properties of ionic and covalent compounds. 4
Ionic compou nds are generally inorganic; have high melting and boiling points due to the strong electrostatic
.~
forces attracting the oppositely charged ions; are soluble in water and insoluble in organic solvents; are hard to bum;
involve reactions that are rapid and simple; also bonds between like elements are rare, with isomerism being unusual.
Covalent compounds, on the other hand, are commonly organic; have relatively low melting and boiling points
because of weak intermolecular forces; are soluble in organic solvents and insoluble in water; bum readily and are
thus susceptible to oxidation because they are less stable to heat, usually decomposing at temperatures above 700°C;
involve reactions that are slow and complex, often needing higher temperatures and/or catalysts, yielding mixtures of
products; also, honds between carbon atoms are typical, with isomerism being common.
1
