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Ltd.net/2027/mdp.TOPICS IN ORGANIC CHEMISTRY Sheldon Emery Professor of Organic Chemistry Harvard University Generated on 2015-08-29 23:09 GMT / http://hdl.org/access_use#pd-google Mary Fieser Research Fellow in Chemistry Harvard University New York REINHOLD PUBLISHING Chapman CORPORATION & Hall..39015007149886 Public Domain. London .hathitrust. Google-digitized / http://www.handle.

hathitrust.Generated on 2015-08-29 23:10 GMT / http://hdl.net/2027/mdp. Google-digitized / http://www.handle.39015007149886 Public Domain.org/access_use#pd-google Copyright © 1963 PRINTED IN THE UNITED STATES by REINHOLD PUBLISHING CORPORATION All rights reserved Library of Congress Catalog Card Number: 63-13444 OF AMERICA .

R and S specification of configuration. It is a pleasure to report that the response was unanimous and that the corrections and suggestions were very helpful.1 refers to the first section of the present book. we decided to bring the book to a close while and length remains to omit several unchanged. Part II includes a few corrections to Advanced and a few topics which should have been included originally (adamantane. Most of the topics concerned are active In under some cases the situation has changed so currently investigation. for fit the the principal journals into framework of Advanced and papers which which seem to us significant and interesting.. The sections of Part I are numbered in extension of those of Advanced for con venience in cross referencing. much in recent years that chapters had to be rewritten in toto or in large part. 3rd edition (1956). The chemistry of rubber is transferred to Terpenoids and the chapter on Synthetic Polymers is limited to man-made elastomers.).handle.hathitrust. arranged according to Much of the chemistry of dyes is historical and polymerization mechanisms. but eventually a plan emerged for combining a revision of the 1956 chapters with a supplementation to the 1961 book. Part I includes nine chapters on subjects which are necessarily specialized but which form important parts of the general field. reference to a specific A cross reference to a page within the present book carries no appendage. chapters or for any imminent extension of the Advanced book. p. special-topic but modern chapters covalently-bonded dyes were introduced less Generated on 2015-08-29 23:10 GMT / http://hdl. the closing date for coverage in Advanced. plastics. e. most of the entries describe advances reported in the literature We have scanned 1. and have included in Part accounts of the new work as supplements to the material previously published.39015007149886 Public Domain.net/2027/mdp. However. As a check on the accuracy of our accounts. We are very much indebted also to the following specialists for reviewing chapters or sections of Part I and presenting invaluable advice : etc. 963. Google-digitized / http://www. since July II iii . We thank the many chemists who contributed in this way to the produc tion of an accurate survey of recent research.org/access_use#pd-google than a decade ago. 1961. nature. and resins.48 designates the last section of Advanced and 32. Thus 31. A page of the first book. 963. The present book is the outcome. copies for review were sent to the principal in vestigator of each research group involved. is entered as Adv.7 PREFACE Having included in the manuscript for Advanced Organic Chemistry (1961) most in beginning and advanced courses of a general of the topics usually considered it was still of reasonable which appeared in Organic At the time we had no plans for revision of these Chemistry. The chapter on Steroids was rewritten in narrative style.g.

J. G. Rogers E. An asterisk is appended to the first entry in the book of the name of a chemist whose biography appears in Advanced Organic Chemistry. E. the short-form journal abbreviations used are listed in the glossary.hathitrust. Lawrence T. as well as corrections and suggestions. Pelletier I. D.iv PREFACE V. Ringold B. Taylor W. M. Part Generated on 2015-08-29 23:10 GMT / http://hdl. Brockmann C. or of the first author listed. W. W. Dermer L. C. Taylor W. Brooks E. Boekelheide J. Lou1s F. Sanderson K. M. Clar A. Quackenbush E. Hochwalt R. Grewe E. F. space-saving References in the text throughout the book follow the style of citing the date and the name of the senior author. C. Google-digitized / http://www. if known to us. I. Nazer for careful reading of the page proof. Seligman We thank Makhluf J. We welcome advice.handle. R. New biographies are included in both Parts I and II. Massachusetts Mary F1eser January 1. C. D. F. W. Herz C. of the present book. J. Cope O. Wildman J. Marion M. Haddadin and Musa Z. The author index provides a guide to biographies published previous in both books.net/2027/mdp. 1963 . E. M.org/access_use#pd-google of recent date and includes authors' names as II is documented with references they appear in the literature. Kuhn E. S. Farkas R. Karrer H. Weedon R. Newman M. Wiesner Leavitt H. van Tamelen P. C. Boothe H. The expense of preparing the many Xerox copies of manuscript that went out for prepublication review was defrayed by a grant from Research Corporation. C. Leete A. V. J. H. A. Herbst W. Hunsberger F. Wenkert R. Fodor Schroeder W. L. Huisgen L.39015007149886 Public Domain. F1eser Cambridge. Ollis I. Softer E. The coverage of the book extends through the major journals which reached us Future plans depend upon the reception of Part II by the date given below. Ugi S.

C Trityl.GLOSSARY SOLVENTS Al Methanol or ethanol Di An Chf Acetone DMF Dimethylformamide H2O Chloroform EtOH Ethanol CgH6 Benzene Hex MeOH Methanol Pyridine Py Hexane Generated on 2015-08-29 23:10 GMT / http://hdl.hathitrust. Ph CH3SO2 Phenyl V Phth Phthaloyl Ph.4-Dinitrofluorobenzene OH+ ArCO3H TsCl />-Toluenesulfonyl chloride TsOH ^-Toluenesulfonic acid W. NBA N-Bromoacetamide NBS N-Bromosuccinimide DNF AcOH Acetic Acid Dioxane Water REACTIONS TNM Tetranitromethane 2.net/2027/mdp.-K.handle.org/access_use#pd-google REAGENTS. (C^3C^-CH3C6HsSO2- . Pr Propyl Ts Tosyl. Wolff-Kishner reduction GROUPS Ac Acetyl Cb Carbobenzoxy /-Bu Et Ethyl /-Butyl Me Methyl Bz Benzoyl Cathyl Carbethoxyl Ms Mesyl.39015007149886 Public Domain. Google-digitized / http://www.

DEVIATIONS 2-Desoxo3-Desoxy- Lacking Lacking Homo. or to the rear No bond configuration unknown epimer mixture £. SYSTEMATIC NAMES A chemical name is divided only when each part is a correctly pronounceable word in its own right.net/2027/mdp. A2-Octene (or 2-octene or octene-2).8-Olefinic derivative Ring D expanded to a six-membered ring Ring A contracted to a five-membered ring Lacking the methyl group at Cn Lacking the methyl group at C1o 2 .vi GLOSSARY CONSTANTS Specific rotation for sodium aD reported as D line at or near 250.3-Seco- 2.39015007149886 Public Domain. endings used as words: diene. Also correct: cholestane-3/3-ol acetate (to be read in the sense "cholestane3/3-ol. triene.hathitrust.(acid) FROM USUAL STRUCTURE a 2-keto group a 3-hydroxyl group CH2CO2H CO2H extended to CH2CO2H CH2CH2CO2H shortened to shortened to CH2CH2CO2H CO2H SPECIFIC TO STEROIDS 7-DehydroD-Homo- A-Nor18-Nor19-Nor2.(acid) Bisnor. or to the front Wavy down.3-dioic 7 .handle. Other 2. of an Frequency.(acid) Nor. cps Cycles per sec. IR absorption band. The same form is appropriate for estrone acetate.3-Bond severed. and is pronounced differently. as is ene. kcal.org/access_use#pd-google 3. ol is a word./lOO. acetate of". Google-digitized / http://www.3-Bond severed and hydrogen added at C2 and C3 2. cholic acid triacetate. diol. The molecular extinc tion coefficient. Molecular rotation (units. MD X cm-1 or wave number. wt. (nuclear magnetic resonance spectra). yl is not a word). Not cholest-5-en-3^-ol (en is not a word. (b) Infrared (IR) absorption maximum in n. (or 5-cholestene-3/3-ol). C2 and C3 converted to CO2H groups . polyol). cortisol 21-acetate. is given in parentheses. (a) Ultraviolet (UV) absorption maximum in rmi determined in ethanol or valid for an ethanolic solution. Cholestanyl acetate. BONDS Full line Dotted line up. e. A6-Cholestene-3/3-ol Generated on 2015-08-29 23:11 GMT / http://hdl. Examples: 1. not degrees) = aD X mol. Not oct-5-ene (oct is not a word).3-Seco-2. or log «. Not cholestan-3/3-yl acetate (cholestan is not a word. conventionally [a]i>./mole Kilogram calories per mole.

handle. now schung) (before World War MPI) Privatdozent of special academic distinction in Germany fessor AG.hathitrust. furane. desoxo. BASF Ciba (Company) Badische Anilin-und Soda-Fabrik (Germany) Gesellschaft fur Chemische Industrie.vii GLOSSARY NOTE ON SPELLING Since chemical names should be and usually are pronounced as they are spelled. we prefer use of dioxane. EUROPEAN TERMS ETH Eidgenossische MPI Institute of Technology) Max-Planck-Institut fur Biochemie KWI Kaiser. tryptophane.net/2027/mdp.Wilhelm-Insti tut Geheimrat Title Habilitationsschrift Independent postdoctoral research publication required for appointment as Privatdozent Post equivalent to that of an assistant or associate pro Technische Zurich Hochschule. Google-digitized / http://www. (Swiss Federal (Medizinische For- II.and deoxy-. since the pronuncia tion is stronger For the same reason we favor than with the -an equivalents. Basel. Switzerland SASM Societe d'Applications scientifique Generated on 2015-08-29 23:11 GMT / http://hdl.over deoxo.org/access_use#pd-google UCLAF Aktiengesellschaft Usines chimiques et mecanique des Laboratoires Francais JOURNALS Journal of the American Chemical Society Angewandte Chemie Annalen der Chemie Annales de chimie (Paris) Chemische Berichte (formerly Berichte der deutschen chemischen Gesellschaft) Bulletin de la societe chimique de France Acta Chemica Scandinavica Collection of Czechoslovak Chemical Communications Comptes rendus hebdomadaires des seances de l'academie des sciences Gazzetta chimica italiana Helvetica Chimica Acta Journal of the Chemical Society (London) Journal of Organic Chemistry Monatshefte fiir Chemie Recueil des travaux chimique des Pays-Bas (The Netherlands) .39015007149886 Public Domain.and desoxy. and urethane.

a mononucleotide dinucleotide Adenosine-5'-triphosphate. the principal biological phosphorylating agent and repository for chemical energy Diphosphopyridine nucleotide (formerly called coenzyme I).39015007149886 Public Domain. AMP ADP ATP Adenosine-5'-monophosphate. a polymer of 2-desoxyribose nucleotide joined together by phosphate linkages be monophosphates tween 3'. a nucleoside adenylic a acid. polymer of ribose nucleotide monophosphates joined together by phosphate linkages between 3'. a dinucleotide composed of AMP FAD joined through a diphosphate linkage to riboflavin-5'-phos- phate FADH Reduced RNA Ribonucleic acid.handle.and 5'-hydroxyl groups Coenzyme A. DPN with an additional phosphate ester group at the 2'-position in the adenosine unit Flavin adenine dinucleotide. a dinucleotide composed of AMP joined through a diphosphate DPN linkage DPNH TPN Reduced to l-/3-D-ribofuranosylnicotinamide-5'-phosphate DPN Triphosphopyridine nucleotide (formerly called coenzyme II). Adenosine-5'-diphosphate. Google-digitized / http://www.hathitrust. which is joined by a peptide link DNA CoASH Generated on 2015-08-29 23:11 GMT / http://hdl. adenylic acid joined through a pyrophosphate linkage to pantothenic acid.viii GLOSSARY BIOCHEMISTRY Adenosine 9-/3-D-Ribofuranosyladenine.net/2027/mdp.and 5'-hydroxyl groups Desoxyribonucleic acid.org/access_use#pd-google FAD a to /3-mercaptoethanol UDPG Uridinediphosphoglucose Pyrimidines: Purines: C Cytosine A Adenine T Thymine : Uracil G Guanine U .

27. Electrophilic 73. Substitution Reactions. Anthraquinones. Rho- 26. Substitutions. 60. 7. 81. 10.39015007149886 Public Domain. Other Phenylpentazole. Naphthaccne. 38. 53. Generated on 2015-08-29 23:11 GMT / http://hdl. Structure and Reactivity. ucts. Chrysene. 24. Hexabenzocoronene. Types.CONTENTS PART 1 Chapter Polynuclear Hydrocarbons Structure. 69. Indole. Triazoles and Tetrazoles. Carcinogenicity and with Chemical Reactivity. thracene. Molecular Overcrowding. domycins. 30. 40. 24. Carcinogenic Structure. 1. Synthetic Routes. 29. Picene. 33. . Griseofulvin. Google-digitized / http://www. Hydrocarbons. Chapter 2 Aromatic Heterocyclic Compounds Five. Pyrrole. 10. Circumanthracene. 65. Hexacene. 20. Furane. Addition 5. 3. 33. 42. 41. Polyunsaturated Derivatives. 66. Triaryltetrazolium Butenolides. 43.net/2027/mdp.hathitrust. 31. Other 6. Cochineal-Carminic Kermes-Kermesic Acid. 59. 79. Benzofuranes. 77.org/access_use#pd-google Polynuclear Pentacene. ix 76. Resonance. Rubrene. Heptacene. Displacement Reactions. Acid. Substitutions. 56. Reaction. Syn 47. Salts. Natural Pig ments. Diels-Alder Pyrrole Pigments. 50. Insect Dyes and Bacterial Pigments. Hydrocarbons. Ring Fission. 63. tion and Synthesis. Coronene. 68. 18. Perylene. 20. Phenanthrene. 71. Oxidation. Lac Dye-Laccaic Acid. 1 Reactions.2-Benzan- 36.and Six Membered Types.handle. Correlation Discovery. Pyrene. 16. thesis. 24. and Thiophene. 27. Reduction Prod Anthracene. 33. 77. 72. Anhydride Synthesis. Succinic 3. 26. Prepara 14.

175. Alkaloid Biosynthesis. Cinchona Alkaloids. 116. Diterpenes (C20). 153. 202. 91. Resin Acids. 123. 172. Pyrones. Hydrocarbons Monocyclic Ketones. Lupine Alkaloids. 86. 101. Tropane Alkaloids. 212. 208. 90. 82. 85. Isomerism. 121. Alkaloids. The Pelletierines. Squalene. lizidines and Phenanthroindolizidines. 184. Bicyclic ds-Terpenes. 142. Google-digitized / http://www. and Aldehydes.net/2027/mdp. Yohimbe Alkaloids. Synthesis of Pyri dines. Acid.org/access_use#pd-google Indole Chapter 4 Terpenoids Isoprene Rule. Oxidation. Quaternary Salts and Hydrox Ring Fission of Pyridinium Salls. 143. Coumarins. Synthesis of Carote . Degradation. Alkaloids. 171. 215. Electrophilic Substitution. Amaryllidaceae Alka Occurrence and 119. 200. 108. 143. Crocetin. 191. 99. 12. Pteridines. Quinoline and Isoquinoline. Chromone. Benzylisoquinolines. Nucleophilic Substitutions and Displacements. 200. Chromane. Khellin. Flavones and Isoflavones. Anthocyanins. 154. 199. Chapter 3 Alkaloids Isolation. noids. Boron Het Pigments. Miscellaneous erocycles. 169. PhenanthroquinoIpecac Alkaloids. Dehydroquinolizinium Salts. Sclareol Group. Calycanthine and Chimonanthine. Preparation. loids. 191. Erythrina Alkaloids. 210. 105. Heterocycles. Rearrangement C1o-Alcohols of Camphor. 179. Bicyclic Terpenes. 200. Cafestol. 117. 202. 145. Cembrene. 205. Ergot Alkaloids. 158. 161. cis-transBixin. Other 103. Pyridine-N-Oxide. 211. 184. 97. 205. 105. Sydnones.CONTENTS X Pyridine. 131. 157. Cantharidin. 98. Triterpenes (C30). Phytol. 222. 192. 211. 147. 202. Carotenes. Morphine. Xanthone. Xanthophyll Alcohols and Epoxides. 127. 155. Ketonic Carotenoids. Carotenoids (C40). Rubber. Sesquiterpenes (Cm). 96. 209. Polycyclic Triterpenoids. Hydroisoquinolines. Ommochromes. Properties. 104. Generated on 2015-08-29 23:11 GMT / http://hdl. Acyclic. Gibberellic Fichtelite. Production of Pyridine Derivatives.hathitrust. 151. (C10). Strychnine. 142. Lycopene. Pyrrolidines. 115. Curare Alkaloids. 159. Terpene 168.39015007149886 Public Domain. 84. 124. 222. 176.handle. ides. 162. 91. 197. Aconite-Garrya Alkaloids. 89. Biosynthesis of Terpenes. Senecio Piperidine Derivatives. Oxindoles. 146. 133. 106. 120.

Macrolides. 334. Riboflavin (Vitamin Vitamin Bs (Pyridoxine). 345. Nicotinic Acid. Hormone Production. 338. Alkaloids.CONTENTS Chapter 5 Steroids 225 and Bile Acids. MelamineUrea-Formaldehyde Resins. 317. Chapter 7 Chemotherapy Organic Arsenicals. change Resins. cin. 293. 339. 291. 340. 288. 351. Polymerization of Dienes. Polyacrylonitrile. logs. Polyacrylates.handle. Radical Polymerization. 277. Adrenocortical Hormones. An 240. Tocopherols. Vitamin A. Antimalarials. Google-digitized / http://www. and Nonactin. 298. 309. 342. Progesterone. Copolymerization. 304 Germanin.39015007149886 Public Domain. Ionic Catalysis. 351. 271. Polyethylene. Estrogens. 319. 339.org/access_use#pd-google Amebicidal Drugs. 328. 325. 356. 344. 318. 344. 325. Polyesters. 327. . 355. 225. 290. 337. 265. Sterols Chapter 6 Vitamins 277 Thiamine (Vitamin B1). 353. Cycloheximide phenicol. Poly ethylene. 336. 313. 287. 342. Neomycins B and C. 244. 251. 253. Polyester Resins. 354. Chapter 8 Synthetic Polymers Polymer Types. Other Sideraminesand Sideromycins. 330. 353. Discovery. 343. PolytetrafluoroPolyvinyl Halides. Vitamin D. Polypeptide Antibiotics. Antibiotics. 318. 231. Physiological Functions of Vitamin A. Biotin. Generated on 2015-08-29 23:12 GMT / http://hdl. Cancer Chemotherapy. Pteroylglutamic Acid. 305. Sulfonamides. 345. 327. Streptomy Chloram Tetracyclines. 282. 280. Ion-Ex Synthetic Resins. 296. Alkyd Resins. 352. Addition Polyurethane Elastomers. Stereospecific Polymerization of Olefins. 320. Actinomycin. 334 Polyamides. Mitomycin A. Phenol-Formaldehyde Resins. Polymerization of Vinyl Monomers. 245. AntimycinA. 284. drogens. 344. 354. Formaldehyde Resins. 286. 262. Condensation Polymerization. 306. Penicillin.net/2027/mdp. Epoxy Resins. 329. Polyoxymethylene. 348. 304. vinyl Acetate. 347. 307. 300. Vitamin K. Polystyrene. 234. 335. Vitamin B12. B2). Pantothenic Acid. Hormone Ana Cardiac Glycosides.hathitrust. 324. 19-Norsteroids.

393.6-Dihalobenzaldehydes. Synthesis of n-Rhamnose.net/2027/mdp. Liquid Ion-Exchange Systems. Lipids of the Honeybee. Selective Chemical Cleavage of Proteins. Dyes. Oxidative Decarboxylation of Alkali Cleavage of Sulfones. Color Photography. 387. Substantive Dyes. Disperse Azo Dyes. 400. Diazirine. 368. 482. 510. quinones. 612. Formation of Dye Mordant Dyeing.handle. Depsipeptides. 358. 381. Twistane. Adamantane. Semicarbazones. Dialkyl 389. Nitration of Ketones. 431. 396. 478. 467. 587. 506. 374. 489. 389. 541. 486. 405. Tyrian Purple. Algol Colors. 390. Phthalocyanines. of Allylic Lichen Dyes. 538. 410. 357 378. 402. Reduction with Diimide.3-Diphenylindenone Oxide. 462. Acetylenic Amines. Synthesis of Acids. of Carbon yl Compounds. 2 . finic Hydroxy Acids. Peptide Synthesis from Acid Hvdrazides. 361. 572. 464. Reduction of Ketones. 617. 390. Benzanthrone 382.xii CONTENTS Chapter 9 Dyes Direct Dyes. 415. 589. Carbazole Types. Dithiazolanthraquinone 387.org/access_use#pd-google (New sections alone are listed here. Google-digitized / http://www. Other Indigoid Dyes. 493. Natural OleVinyl Ketone Synthesis of Acids. PART 2 Generated on 2015-08-29 23:12 GMT / http://hdl. Synthetic Alizarin.) R and S Specification of Configurations. DipyrazolanAnthranthrone Tetracarboxyimide Dyes. Sulfur Dyes. 553. 448. 456. Chrome Dyes. 367. Perkin's Mauve. on the Fiber. Thiophene Synthesis of Arachidonic Acid. Lacquer Pigments. Dyes. Dyes. 389. 463. Hydrogenolysis. thrones. 360. Scent Attractants and Repellents of Insects. 596. Dyes. 371.hathitrust. Cleavage of Phenylhydrazones and Enol Ethers./3-Oxido Ketones. 360.39015007149886 Public Domain. 593. 578. Cyanine Dyes. 378. Phosphonate Modification of the Wittig Reaction. Color and Constitution. 362. 584. 363. 545. Optically Active Cycloalkenes and Aromatic Hydrocarbons from 2-Pyrones. 407. Kallidin and Bradykinin. 415. 432. Reduction of a . Brighteners. 364. 422. 411. 556. 487. Light-Catalyzed Dienes. 610. 404. The Phthaleins. 512. 391. Distribution of Fatty Acids in Natural Glycerides. Indanthrone. 357. Reactive Dyes. Anthraquinone Dyes for Wool and for Hydrophobic Fibers. Acidic and Basic Azo Dyes. 536. Aurin. Azoic Substantive Azo Dyes. 384. of Esters. Printing. Vat Dyeing. Pseudoaromatic Heterocycles. Diaza2 . Flavanthrone. 590. 519. Peroxidation of Ketones. 613. Diazacyanines. 375. 591. Polyhydroxyanthraquinones. 459. 362. Synthetic Indigo. Dibenzpyrenequinones. Octaphenylcubane. 413. . Ethylation of Amines. 581. Imidazolide Synthesis Trishomocyclopropenyl Cation. Rosaniline Dyes. Rearrangement Rearrangement Acids. 373. 554.