Transition metal complexes 1042 Stereochemistry of homogeneous hydrogenation: diastereoselectivity 1046 Stereochemistry of homogeneous hydrogenation: \u20acnantioselectivity 1049 The oxo process 1052 Enzyme action 1054 29.s 29.6 29.7 29.8 29.9 3A HeterocycHc ConPounds 30.1 Heterocyclic systems 1457 FIVE.MBMBERED RINGS 30.2 30.3 30.4 Structure of pyrrole, furan, and thiophene 1059 Source of pynole, furan, and thiophene 1061 Electrophdic substitution in pyrrole, furan, and thiophene. Reactivity and orientation 1062 31 CONTENTS 30.5 Saturatedfive-memberedheterocycles 1065 SIX-MEMBERED RINGS 30.6 Structure of pyridine 1066 30.7 Source of pyridine compounds 1067 30.8 Reactions of pyridine 106g 30.9 Electrophilis substitution in pyridine 106g 30.10 Nucleophilic substitution in pyridine 1069 30.1 I Basicity of pyridine t07I 30.12 Reduction of pyridine 1073 Macromolecules. Polymers and polymerization 31.1 Macromolecules 1077 31.2 Polymers and polymerization I07g 31.3 Free-radical vinyl polymerization I0g0 31.4 Copolymerization l0B3 ?1.5 Ionic polymerization. Living polymen I0g431.6 Coordination polymerization |OAZ 31,7 Stepreactionpolymerization I0g0 31.8 Structure and properties of macromolecules l0g3 ste_reochemistry- III. Enantiotopii and Diastereotopic Ligands and Faces 32.1 Introduction I I0l 32.2 Biological oxidation and reduction. Ethanol and acetaldehyde I ILt 32.3 Biological oxidation and reduction. Deuterium labeling experiments 1103 3?.4 Biological oxidation and reduction. stereochemistry l I04 125J Enantiotopic and diastereotopic ligands I I0732.6 Enantiotopic and diastereotopic faces I I t0 32.7 Origln ofienantiospecificity I I 12 PART THREE Biomolecules 33 Lipids Fats s.nd Steroids 33.1 The organic chemistry of biomolecules I I Ig 33.2 Lipids 1120 33.3 Occurrence and composition of fats I I 20 33.4 Hydrolysis of fats. Soap. Micelles I I24 33.5 Fats as souroes of pure acids and alcohols t I2S 33.6 Detergents 1126 33.7 Unsaturated fats. H4rdening of oils. Drying oils II27 33.8 Phosphoglycerides.phosphateesterr. IltS 33.9 Phospholipids and cell membraqes IIJ| 32 CONTENTS 33.10 Biosynthesis of fatty.aoids 1132 33.11 Steroids 1134 34 Carbohydrates I. Monosaccharides Introduction 1143 Definition and classification (*)-Glucose: an aldohexose (-)-Fructose: a 2-ketohexose Stereoisomers of (*)-glucose. derivatives 1146 Oxidation. Effect of alkali 1149 Osazone formation. EPimers I 151 Lengthening the carbon chain of aldoses. The Kiliani-Fischer synthesis I 152 Shortening the carbon chain of aldoses' The Ruff degradation 1154 Conversion of an aldose into its epimer 1154 Configuration of (*)-glucose. The Fischer proof I155 Configurations ofaldoses 1160 Optical families. o and t- 1162 Tartaric acid 1164 Families of aldoses. Absolute configuration 1166-Cv.ii. rir".,"re of o-(*)-glupose. Formation of glucosides 1168 Configuration about C-1 1173 Methylation 1174 Determination of ring size I176 Conformation 1178 34.r 34.2 34.3 34.4 34.5 34.6 34;7 34.8 34.9 34.10 34.1r 34.r2 34.r3 34.14 34.r5 34.16 34.r7 34.18 34.t9 34.20 I 144 I 144 1 146 Nomenclature of aldose 35 carbohydrates II. Disaccharides and Polysaccharides 35.I Disaccharides l18f 35.2 (*)-Maltose 1185 35.3 (*)-Cellobiose 1188 35.4 (*)-Lactose 1j,89 35.5 (*)-Sucrose 1191 35.6 Polysaccharides 1192 35.7 Starch 1193 35.8 Structure of amylose. End group analysis /,193 35.9 Structure of amYloPectin 1195 35.10 CYclodextrins 1198 35.1I Structure of cellulose 1200 35.12 Reactions of cellulose 1200 36 Proteins and Nucleic Acids Molecular Biology 36.1 Proteins 1205 36.2 Structure of amino acids 1206 36.3 Amino acids as dipolar ions 1208 36.4 Isoelectric point of amino acids 1211 36.5 36.6 36.7 36,p 36,9 36.10 35.1 1 36.12 36.t3 36.r4 36.1 5 36.r6 36.17 36.r8 36.t9 36.20 CONTENTS @Ohfigurationof natural amino acids I2t2 Pireparation of amino acids l2I3 Reactions of amino acids l2ts Pepqides. Gdometry of the peptide linkage l2Is Doremrinadon of structure of peptides. Terminal residue analysls. Partial hydrolysis I2I7 Synthesis ofpeptides 1221 Proteins. Classification and function. Denaturation I22S Structure of proteins 1226 Peptide chain 1226 Side chains. Isoelectnc poinl Electrophoresis 1227 Conjugated proteins. Prosthetic groups. Coenzymes l22g Secondary structure ofproteins l22g Biochemistry, molecular biology, and organic chemistry I2JJ Mechanism of enzyme action. Chymotrypsin 1236 ' Nucleoprciteins and nucleic acids t24l Chemistry and heredity. The genetic code 1246 Suggested Readings 12SI Answers to Problems 1263 Index 1279 Preface Perhaps the only thing that teachers of organic chemistry today are agreed on is ttrat ttre textbooks -have frown too big. And they have - including our own' And *, *t.fti"f airn in prepaiing this sixth edition was to shorten the book' We havc ;;;; 150 pages iiom it aid, most important, have rewritten the early chaptcn to -"te ttris funaamental material more accesible to the student. In shortening the book, however, we have stuck to the principle we hlve always held: thesi are beginning styde.nts, and they need all the help they can get' When we take up a topiC we eiplain it as fully and clearly as we can; the book is shorter simply because we take up iewer topics' A oo-G, of chapters have disappeared, as chapters. Some of their content has been moved to otlier chapters. Some has been presented as problems, and is "-pf"io.A it the Study Guidi; this material is thus available to help students to Uto"O.o their understanding of organic chemistry beyond the limits of the text- book. Much has been delrt"i *og"tfter as being less important than new material that replaces it.---- it. systematic treatment of alcohols and ethers has been moved fonn'ard to Ct apte.O, Jn"re it immediately follows the chapter on alkyl halides. Introduced "itfri,5 poioq the chemistry of alcohols gives students the opportunity to apply aj.d buitd onwhat they have just been studying about nucleophilic substitution' They see Acofrofs x sibstratis, as nucleophiles, and as teavilts q;ou7s' They are intro- ["."Oto the most important-andsimplest-catalytic efect in orpnic chemis" ti, iiri*ion. (In ihapter 7, alcotrols will appear again, playing still another star ;;-i; ;;;iropttiti. subititution: that of solvent.) With the most important labo-'oto.y *utr. of aipn"ti. compounds in their hands, students can begin to carry out organic synthesis in a realistic way' Thirty-odd yean ago, when our fint edition appeared, it was a slim volume of onlyg00p"go.Yet,inouropinion-then,andnow-itpfettJwellpresented Gi" o"gu-"iichemistry as it was then: a science whose theory had come of age and *"fO d understoodland enjoyed-by begrnners. The pattern underlying or- g""i. .ft .irtry had begun to emerge,^ and it was our aim to reveal it to the i.rO"ott. With the structurat theory before them, it soon became apparent' stu- xxtv PREFACE dents could begin to.study organic chemistry, not through rote rnemorization, butthrough/ under s t anding. But organic chemistry has, of course, continud to grow, and at a tremendous r4te, Theories have been refined and exceptions to geniralizations found; tniog, are not so simple as they once seemed. New concepts and new tools have appearei and established themselves as part of basic organic chemistry: orbital s6;.t.y,for example, or nuclear magnetic resonance. Vtany factors have been found to be much more important than was previously realized: the role ofthe solvent, stereo- chemistry in all its aspects, the juxtaposition of reacting grorrpr. Hosts of new reaBents have been devised: chemoselective, regioselectiieJtereoselective. with all this grofih, the pattern underlying organic chemistry has becomebroader and more complex.