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THEORY 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 McGRAW-HILL New York San Francisco Washington, D.C. Auckland Bogoth Caracas Lisbon London Madrid Mexico City Milan Montreal New Delhi San Juan Singapore Sydney Tokyo Toronto 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 Production Supervisor: Shem Souffrance Editing Supervisor: Maureen Walker Project Management: Techset Composition Limited 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