Instant Notes Organic Chemistry SECOND EDITION G.Patrick Also available as a printed book see title verso for ISBN details
This edition published in the Taylor&Francis e-Library.2005. "To purchase your own copy of this or any of Taylor&Francis or Routledge's collection of thousands of eBooks please go to www.eBookstore.tandf.co.uk." Garland science/Bios Scientific publishers.2004 First published 2000 Second edition published 2004 All rights rese ved.No part of this book may be reproduced or transmitted,in any form or by any means without permission. A CIP catalogue record for this book is available from the British Library. ISBN 0-203-42761-0 Master e-book ISBN 030344168.0 Garland Science/BIOS Scientific Publisher 4 Park Sq are,Milton Park,Abingdon,Oxon OX14 4RN,UK and 2 West 3th Street.New York,NY 10019.USA World Wide Web home page:www.bios.co.uk Garland Science/BIOS Scientific Publishers is a member of the Taylor&Francis Group Distributed in the USA by Taylor 10650 Toebben Drive Distributed in Canada by Taylor Francis 74 Rolark Drive Distributed in the rest of the world by Thomson Publishing Services North Way Andover,Hampshire SP10 5BE,UK Tel:+44(0)1264 332424;E-mail:salesorder.tandf@thomsonpublishingservices.co.uk Library of Congress Cataloging-in-Publication Data Patrick,Graham L Organic chemistry /G.L Patrick-2nd ed. ISBN-25lk Paper) sand inde 022x72 Production Editor:Andrew Watts
© Garland Science/BIOS Scientific Publishers, 2004 First published 2000 Second edition published 2004 All rights reserved. No part of this book may be reproduced or transmitted, in any form or by any means, without permission. A CIP catalogue record for this book is available from the British Library. ISBN 1 85996 264 5 Garland Science/BIOS Scientific Publishers 4 Park Square, Milton Park, Abingdon, Oxon OX14 4RN, UK and 29 West 35th Street, New York, NY 10001–2299, USA World Wide Web home page: www.bios.co.uk Garland Science/BIOS Scientific Publishers is a member of the Taylor & Francis Group Distributed in the USA by Fulfilment Center Taylor & Francis 10650 Toebben Drive Independence, KY 41051, USA Toll Free Tel.: +1 800 634 7064; E-mail: taylorandfrancis@thomsonlearning.com Distributed in Canada by Taylor & Francis 74 Rolark Drive Scarborough, Ontario M1R 4G2, Canada Toll Free Tel.: +1 877 226 2237; E-mail: tal_fran@istar.ca Distributed in the rest of the world by Thomson Publishing Services Cheriton House North Way Andover, Hampshire SP10 5BE, UK Tel.: +44 (0)1264 332424; E-mail: salesorder.tandf@thomsonpublishingservices.co.uk Library of Congress Cataloging-in-Publication Data Patrick, Graham L. Organic chemistry / G.L. Patrick.—2nd ed. p. cm. — (Instant notes series) Includes bibliographical references and index. ISBN 1-85996-264-5 (alk. paper) 1. Chemistry, Organic—Outlines, syllabi, etc. I. Title: Instant notes organic chemistry. II. Title. III. Series. QD256.5.P37 2003 547—dc22 Production Editor: Andrew Watts This edition published in the Taylor & Francis e-Library, 2005. "To purchase your own copy of this or any of Taylor & Francis or Routledge's collection of thousands of eBooks please go to www.eBookstore. ISBN 0-203-42761-0 Master e-book ISBN ISBN 0-203-44168-0 (Adobe eReader Format) (Print Edition) tandf.co.uk
CONTENTS Preface Section A-Structure and bonding Atomic structure of carbon 1 AI gand hybridization sp 3 sp 公 Section B-Alkanes and cycloalkanes 19 B1 Definition B2 Drawing structures B3 Nomenclature Section C-Functional groups C1 Recognition of functional groups Aliphatic and aromatic functional groups Intermolecular bonding 779035 compounds with functional groups Section D-Stereochemistry D1 Constitutional isomers D2 Configurational isomers-alkenes and cycloalkanes D3 Configurational isomers-optical isomers D4 Conformational isomers Section E-Nucleophiles and electrophiles 63 Definition Charged species Neutral inorganic species Organic structures Section F-Reactions and mechanisms Mechanisms Section G-Acid-base reactions G1 Bronsted-Lowry acids and bases 79 G2 Acid strength G3 Base strength Lewis acids and bases Enolates
Preface ix Section A – Structure and bonding 1 A1 Atomic structure of carbon 1 A2 Covalent bonding and hybridization 3 A3 sp3 Hybridization 5 A4 sp2 Hybridization 8 A5 sp Hybridization 14 A6 Bonds and hybridized centers 17 Section B – Alkanes and cycloalkanes 19 B1 Definition 19 B2 Drawing structures 20 B3 Nomenclature 22 Section C – Functional groups 27 C1 Recognition of functional groups 27 C2 Aliphatic and aromatic functional groups 29 C3 Intermolecular bonding 30 C4 Properties and reactions 33 C5 Nomenclature of compounds with functional groups 35 C6 Primary, secondary, tertiary and quaternary nomenclature 43 Section D – Stereochemistry 45 D1 Constitutional isomers 45 D2 Configurational isomers – alkenes and cycloalkanes 46 D3 Configurational isomers – optical isomers 49 D4 Conformational isomers 56 Section E – Nucleophiles and electrophiles 63 E1 Definition 63 E2 Charged species 64 E3 Neutral inorganic species 66 E4 Organic structures 69 Section F – Reactions and mechanisms 73 F1 Reactions 73 F2 Mechanisms 75 Section G – Acid–base reactions 79 G1 Brønsted–Lowry acids and bases 79 G2 Acid strength 82 G3 Base strength 88 G4 Lewis acids and bases 94 G5 Enolates 95 CONTENTS
Contents Section H-Alkenes and alky repa 990 sym metric al alke op insymmet nes 112 cation stabilization 115 H6 Reduction and oxidation of alkenes 117 H7 Hydroboration of alkenes 121 H8 Electrophilic additions to alkynes 124 H9 Reduction of alkynes 127 H10 Alkylation of terminal alkynes 129 H11 Conjugated dienes Section I- Aromatic chemistry 185 of honz ne 139 is of m 147 Electrophilic substitutions of mono-substituted aromatic rings 150 Synthesis of di-and tri-substituted benzenes 160 7 Oxidation and reduction 164 Section] Aldehydes and ketones 167 Preparat on ilic additi ilic ad arged nucleophiles Nucleon ogen nucleophiles and sulf 187 Reactions of enolate ions g-Halogenation 198 Reduction and oxidation I11 aB-Unsaturated aldehvdes and ketones 202 Section K-Carboxylic acids and carboxylic acid derivatives 205 KI and 205 K2 209 K3 Reactivity 213 K4 Preparations of carboxylic acids 217 K5 Preparations of carboxylic acid derivatives 219 K6 Reactions 224 K7 Enolate reactions 234 Section L-Alkyl halides 1 and physical properties of alkyl halides ohilic suhs ution 242 3 Factors affecting S2 versus S1 reactions 247 Elimination 252 Elimination versus substitution 256 L6 Reactions of alkyl halides 258 Organometallic reactions 261
Section H – Alkenes and alkynes 99 H1 Preparation of alkenes and alkynes 99 H2 Properties of alkenes and alkynes 101 H3 Electrophilic addition to symmetrical alkenes 105 H4 Electrophilic addition to unsymmetrical alkenes 112 H5 Carbocation stabilization 115 H6 Reduction and oxidation of alkenes 117 H7 Hydroboration of alkenes 121 H8 Electrophilic additions to alkynes 124 H9 Reduction of alkynes 127 H10 Alkylation of terminal alkynes 129 H11 Conjugated dienes 131 Section I – Aromatic chemistry 135 I1 Aromaticity 135 I2 Preparation and properties 137 I3 Electrophilic substitutions of benzene 139 I4 Synthesis of mono-substituted benzenes 147 I5 Electrophilic substitutions of mono-substituted aromatic rings 150 I6 Synthesis of di- and tri-substituted benzenes 160 I7 Oxidation and reduction 164 Section J – Aldehydes and ketones 167 J1 Preparation 167 J2 Properties 169 J3 Nucleophilic addition 173 J4 Nucleophilic addition – charged nucleophiles 175 J5 Electronic and steric effects 181 J6 Nucleophilic addition – nitrogen nucleophiles 184 J7 Nucleophilic addition – oxygen and sulfur nucleophiles 187 J8 Reactions of enolate ions 191 J9 α-Halogenation 198 J10 Reduction and oxidation 200 J11 α,β-Unsaturated aldehydes and ketones 202 Section K – Carboxylic acids and carboxylic acid derivatives 205 K1 Structure and properties 205 K2 Nucleophilic substitution 209 K3 Reactivity 213 K4 Preparations of carboxylic acids 217 K5 Preparations of carboxylic acid derivatives 219 K6 Reactions 224 K7 Enolate reactions 234 Section L – Alkyl halides 239 L1 Preparation and physical properties of alkyl halides 239 L2 Nucleophilic substitution 242 L3 Factors affecting SN2 versus SN1 reactions 247 L4 Elimination 252 L5 Elimination versus substitution 256 L6 Reactions of alkyl halides 258 L7 Organometallic reactions 261 vi Contents
Contents Section M-Alcohols.phenols.and thiols M2 paration of phenols M3 Pro perties of alcohols and phenols 266 M4 Reactions of alcohols 270 M5 Reactions of phenols M6 Chemistry of thiols Section N-Ethers,epoxide and thioeth repar s,epoxide and thioethers 283 Section O-Amines and nitriles 29 OT Preparation of amines 02 Properties of amines Reactions of amines 03 04 Chemistry of nitriles 311 Section P-Organic spectroscopy and analysis ult a violet spectroscopy 317 P3 Infra-red s 322 Proton nuclear etic resonance spectroscopy 324 P5 C nuclear magnetic resonance spectroscopy P6 342 Further reading Index 34
Section M – Alcohols, phenols, and thiols 263 M1 Preparation of alcohols 263 M2 Preparation of phenols 264 M3 Properties of alcohols and phenols 266 M4 Reactions of alcohols 270 M5 Reactions of phenols 277 M6 Chemistry of thiols 281 Section N – Ethers, epoxides, and thioethers 283 N1 Preparation of ethers, epoxides, and thioethers 283 N2 Properties of ethers, epoxides, and thioethers 286 N3 Reactions of ethers, epoxides, and thioethers 289 Section O – Amines and nitriles 295 O1 Preparation of amines 295 O2 Properties of amines 299 O3 Reactions of amines 305 O4 Chemistry of nitriles 311 Section P – Organic spectroscopy and analysis 315 P1 Spectroscopy 315 P2 Visible and ultra violet spectroscopy 317 P3 Infra-red spectroscopy 322 P4 Proton nuclear magnetic resonance spectroscopy 324 P5 13C nuclear magnetic resonance spectroscopy 339 P6 Mass spectroscopy 342 Further reading 347 Index 349 Contents vii